Hello,
I have the same problem, the TLS work fine for the request of the mail and
for send the mail but not for the DKIM relay.
I tried with a self-signed certificate and with a CA signed certificate but
none of them solve it.

here is my postconf -n, I changed my domains names:"dns.name.tld" is my
postfix and "dns.name2.tld" is my main domain

2bounce_notice_recipient = postfixrepo...@dns.name2.tld
alias_database = hash:/etc/aliases
alias_maps = hash:/etc/aliases
append_dot_mydomain = no
biff = no
bounce_notice_recipient = postfixrepo...@dns.name2.tld
bounce_queue_lifetime = 1d
broken_sasl_auth_clients = yes
config_directory = /etc/postfix
content_filter = dksign:[127.0.0.1]:12027
cyrus_sasl_config_path = /etc/postfix/sasl
home_mailbox = Maildir/
inet_interfaces = all
mailbox_command = 
mailbox_size_limit = 0
maximal_queue_lifetime = 1d
mydestination = localhost, localhost.localdomain
myhostname = dns.name.tld
mynetworks = 127.0.0.0/8 [::ffff:127.0.0.0]/104 [::1]/128 192.168.0.0/24
192.168.10.0/24 192.168.20.0/24 192.168.30.0/24
myorigin = /etc/mailname
notify_classes = resource, software
readme_directory = no
recipient_delimiter = +
relayhost = 
smtp_starttls_timeout = 60s
smtp_tls_CAfile = /etc/ssl/certs/ca-certificates.crt
smtp_tls_cert_file = /etc/ssl/certs/postfix.crt
smtp_tls_key_file = /etc/ssl/private/postfix.key
smtp_tls_loglevel = 2
smtp_tls_scert_verifydepth = 5
smtp_tls_security_level = may
smtp_tls_session_cache_database = btree:${data_directory}/smtp_scache
smtp_use_tls = yes
smtpd_banner = $myhostname ESMTP $mail_name (Debian/GNU)
smtpd_recipient_restrictions = permit_mynetworks, 
permit_sasl_authenticated,  reject_non_fqdn_hostname, 
reject_non_fqdn_sender,  reject_non_fqdn_recipient,   
reject_unauth_destination,  reject_unauth_pipelining,    
reject_invalid_hostname,  reject_rbl_client list.dsbl.org, 
reject_rbl_client bl.spamcop.net,  reject_rbl_client sbl-xbl.spamhaus.org
smtpd_sasl_auth_enable = yes
smtpd_sasl_local_domain = $myhostname
smtpd_sasl_security_options = noanonymous
smtpd_sasl_type = cyrus
smtpd_starttls_timeout = 60s
smtpd_tls_CAfile = /etc/ssl/certs/ca-certificates.crt
smtpd_tls_cert_file = /etc/ssl/certs/postfix.crt
smtpd_tls_key_file = /etc/ssl/private/postfix.key
smtpd_tls_loglevel = 2
smtpd_tls_received_header = yes
smtpd_tls_session_cache_database = btree:${data_directory}/smtpd_scache
smtpd_tls_session_cache_timeout = 3600s
smtpd_use_tls = yes
tls_random_source = dev:/dev/urandom
transport_maps = hash:/etc/postfix/transport
virtual_alias_maps = mysql:/etc/postfix/mysql_virtual_alias_maps.cf
virtual_gid_maps = static:5000
virtual_mailbox_base = /home/vmail
virtual_mailbox_domains = mysql:/etc/postfix/mysql_virtual_domains_maps.cf
virtual_mailbox_limit = 51200000
virtual_mailbox_maps = mysql:/etc/postfix/mysql_virtual_mailbox_maps.cf
virtual_minimum_uid = 5000
virtual_transport = virtual
virtual_uid_maps = static:5000

Here is my master.cf

#
# Postfix master process configuration file.  For details on the format
# of the file, see the master(5) manual page (command: "man 5 master").
#
# Do not forget to execute "postfix reload" after editing this file.
#
# ==========================================================================
# service type  private unpriv  chroot  wakeup  maxproc command + args
#               (yes)   (yes)   (yes)   (never) (100)
# ==========================================================================
# relayer sur dksign sur le port 10028
smtp      inet  n       -       -       -       200     smtpd
        -o receive_override_options=no_address_mappings
        -o content_filter=dksign:[127.0.0.1]:12027

smtps     inet  n       -       -       -       -       smtpd
  -o smtpd_tls_wrappermode=yes
  -o smtpd_sasl_auth_enable=yes
  -o content_filter=dksign:[127.0.0.1]:12027
  -o receive_override_options=no_address_mappings
  -o
smtpd_client_restrictions=permit_mynetworks,permit_sasl_authenticated,reject

submission  inet  n     -       n       -       -       smtpd
    -o smtpd_etrn_restrictions=reject
    -o smtpd_sasl_auth_enable=yes
    -o content_filter=dksign:[127.0.0.1]:12027
    -o receive_override_options=no_address_mappings
    -o
smtpd_recipient_restrictions=permit_mynetworks,permit_sasl_authenticated,reject
    #-o
smtpd_recipient_restrictions=permit_mynetworks,permit_sasl_authenticated,reject
#628       inet  n       -       -       -       -       qmqpd
pickup    fifo  n       -       -       60      1       pickup
cleanup   unix  n       -       -       -       0       cleanup
qmgr      fifo  n       -       n       300     1       qmgr
#qmgr     fifo  n       -       -       300     1       oqmgr
tlsmgr    unix  -       -       -       1000?   1       tlsmgr
rewrite   unix  -       -       -       -       -       trivial-rewrite
bounce    unix  -       -       -       -       0       bounce
defer     unix  -       -       -       -       0       bounce
trace     unix  -       -       -       -       0       bounce
verify    unix  -       -       -       -       1       verify
flush     unix  n       -       -       1000?   0       flush
proxymap  unix  -       -       n       -       -       proxymap
proxywrite unix -       -       n       -       1       proxymap
smtp      unix  -       -       -       -       -       smtp
# When relaying mail as backup MX, disable fallback_relay to avoid MX loops
relay     unix  -       -       -       -       -       smtp
        -o smtp_fallback_relay=
#       -o smtp_helo_timeout=5 -o smtp_connect_timeout=5
showq     unix  n       -       -       -       -       showq
error     unix  -       -       -       -       -       error
retry     unix  -       -       -       -       -       error
discard   unix  -       -       -       -       -       discard
local     unix  -       n       n       -       -       local
virtual   unix  -       n       n       -       -       virtual
lmtp      unix  -       -       -       -       -       lmtp
anvil     unix  -       -       -       -       1       anvil
scache    unix  -       -       -       -       1       scache
#
# ====================================================================
# Interfaces to non-Postfix software. Be sure to examine the manual
# pages of the non-Postfix software to find out what options it wants.
#
# Many of the following services use the Postfix pipe(8) delivery
# agent.  See the pipe(8) man page for information about ${recipient}
# and other message envelope options.
# ====================================================================
#
# maildrop. See the Postfix MAILDROP_README file for details.
# Also specify in main.cf: maildrop_destination_recipient_limit=1
#
maildrop  unix  -       n       n       -       -       pipe
  flags=DRhu user=vmail argv=/usr/bin/maildrop -d ${recipient}
#
# ====================================================================
#
# Recent Cyrus versions can use the existing "lmtp" master.cf entry.
#
# Specify in cyrus.conf:
#   lmtp    cmd="lmtpd -a" listen="localhost:lmtp" proto=tcp4
#
# Specify in main.cf one or more of the following:
#  mailbox_transport = lmtp:inet:localhost
#  virtual_transport = lmtp:inet:localhost
#
# ====================================================================
#
# Cyrus 2.1.5 (Amos Gouaux)
# Also specify in main.cf: cyrus_destination_recipient_limit=1
#
#cyrus     unix  -       n       n       -       -       pipe
#  user=cyrus argv=/cyrus/bin/deliver -e -r ${sender} -m ${extension}
${user}
#
# ====================================================================
# Old example of delivery via Cyrus.
#
#old-cyrus unix  -       n       n       -       -       pipe
#  flags=R user=cyrus argv=/cyrus/bin/deliver -e -m ${extension} ${user}
#
# ====================================================================
#
# See the Postfix UUCP_README file for configuration details.
#
uucp      unix  -       n       n       -       -       pipe
  flags=Fqhu user=uucp argv=uux -r -n -z -a$sender - $nexthop!rmail
($recipient)
#
# Other external delivery methods.
#
ifmail    unix  -       n       n       -       -       pipe
  flags=F user=ftn argv=/usr/lib/ifmail/ifmail -r $nexthop ($recipient)
bsmtp     unix  -       n       n       -       -       pipe
  flags=Fq. user=bsmtp argv=/usr/lib/bsmtp/bsmtp -t$nexthop -f$sender
$recipient
scalemail-backend unix  -       n       n       -       2       pipe
  flags=R user=scalemail argv=/usr/lib/scalemail/bin/scalemail-store
${nexthop} ${user} ${extension}
mailman   unix  -       n       n       -       -       pipe
  flags=FR user=list argv=/usr/lib/mailman/bin/postfix-to-mailman.py
  ${nexthop} ${user}



dksign  unix    -       -       n       -       10      smtp
         -o smtp_send_xforward_command=yes
         -o smtp_discard_ehlo_keywords=8bitmime

127.0.0.1:12028 inet    n       -       n       -       10      smtpd
         -o content_filter=
         -o
receive_override_options=no_unknown_recipient_checks,no_header_body_checks
         -o smtpd_helo_restrictions=
         -o smtpd_client_restrictions=
         -o smtpd_sender_restrictions=
         -o smtpd_recipient_restrictions=permit_mynetworks,reject
         -o mynetworks=127.0.0.0/8
         -o smtpd_authorized_xforward_hosts=127.0.0.0/8

And a log that show the sending of a mail:

Jul 23 17:03:21 PC1 postfix/smtpd[26335]: initializing the server-side TLS
engine
Jul 23 17:03:21 PC1 postfix/smtpd[26335]: connect from
dns.name.tld[xxx.xxx.xxx.xxx]
Jul 23 17:03:23 PC1 postfix/smtpd[26335]: setting up TLS connection from
dns.name.tld[xxx.xxx.xxx.xxx]
Jul 23 17:03:23 PC1 postfix/smtpd[26335]: dns.name.tld[xxx.xxx.xxx.xxx]: TLS
cipher list "ALL:+RC4:@STRENGTH"
Jul 23 17:03:23 PC1 postfix/smtpd[26335]: SSL_accept:before/accept
initialization
Jul 23 17:03:23 PC1 postfix/smtpd[26335]: SSL_accept:SSLv3 read client hello
B
Jul 23 17:03:23 PC1 postfix/smtpd[26335]: SSL_accept:SSLv3 write server
hello A
Jul 23 17:03:23 PC1 postfix/smtpd[26335]: SSL_accept:SSLv3 write certificate
A
Jul 23 17:03:23 PC1 postfix/smtpd[26335]: SSL_accept:SSLv3 write key
exchange A
Jul 23 17:03:23 PC1 postfix/smtpd[26335]: SSL_accept:SSLv3 write server done
A
Jul 23 17:03:23 PC1 postfix/smtpd[26335]: SSL_accept:SSLv3 flush data
Jul 23 17:03:24 PC1 postfix/smtpd[26335]: SSL_accept:SSLv3 read client key
exchange A
Jul 23 17:03:24 PC1 postfix/smtpd[26335]: SSL_accept:SSLv3 read finished A
Jul 23 17:03:24 PC1 postfix/smtpd[26335]: SSL_accept:SSLv3 write session
ticket A
Jul 23 17:03:24 PC1 postfix/smtpd[26335]: SSL_accept:SSLv3 write change
cipher spec A
Jul 23 17:03:24 PC1 postfix/smtpd[26335]: SSL_accept:SSLv3 write finished A
Jul 23 17:03:24 PC1 postfix/smtpd[26335]: SSL_accept:SSLv3 flush data
Jul 23 17:03:24 PC1 postfix/smtpd[26335]: Anonymous TLS connection
established from dns.name.tld[xxx.xxx.xxx.xxx]: TLSv1 with cipher
DHE-RSA-AES256-SHA (256/256 bits)
Jul 23 17:03:28 PC1 postfix/smtpd[26335]: 1AB4128411E:
client=dns.name.tld[xxx.xxx.xxx.xxx], sasl_method=PLAIN,
sasl_username=m...@my.domain.tld
Jul 23 17:03:29 PC1 postfix/cleanup[26340]: 1AB4128411E:
message-id=<51ee9b3a.9040...@my.domain.tld>
Jul 23 17:03:29 PC1 postfix/qmgr[26257]: 1AB4128411E:
from=<m...@my.domain.tld>, size=738, nrcpt=1 (queue active)
Jul 23 17:03:29 PC1 postfix/smtp[26341]: initializing the client-side TLS
engine
Jul 23 17:03:29 PC1 postfix/smtpd[26342]: initializing the server-side TLS
engine
Jul 23 17:03:29 PC1 postfix/smtpd[26342]: connect from
localhost.localdomain[127.0.0.1]
Jul 23 17:03:29 PC1 postfix/smtp[26341]: discarding EHLO keywords: 8BITMIME
Jul 23 17:03:29 PC1 postfix/smtpd[26342]: setting up TLS connection from
localhost.localdomain[127.0.0.1]
Jul 23 17:03:29 PC1 postfix/smtpd[26342]: localhost.localdomain[127.0.0.1]:
TLS cipher list "ALL:+RC4:@STRENGTH"
Jul 23 17:03:29 PC1 postfix/smtp[26341]: setting up TLS connection to
127.0.0.1[127.0.0.1]:12027
Jul 23 17:03:29 PC1 postfix/smtpd[26342]: SSL_accept:before/accept
initialization
Jul 23 17:03:29 PC1 postfix/smtp[26341]: 127.0.0.1[127.0.0.1]:12027: TLS
cipher list "ALL:+RC4:@STRENGTH"
Jul 23 17:03:29 PC1 postfix/smtp[26341]: looking for session
dksign:127.0.0.1:12027:my.domain.tld&p=1&c=ALL:+RC4:@STRENGTH in smtp cache
Jul 23 17:03:29 PC1 postfix/tlsmgr[26264]: lookup smtp session
id=dksign:127.0.0.1:12027:my.domain.tld&p=1&c=ALL:+RC4:@STRENGTH
Jul 23 17:03:29 PC1 postfix/smtp[26341]: SSL_connect:before/connect
initialization
Jul 23 17:03:29 PC1 postfix/smtp[26341]: SSL_connect:SSLv2/v3 write client
hello A
Jul 23 17:03:31 PC1 postfix/smtpd[26335]: disconnect from
dns.name.tld[xxx.xxx.xxx.xxx]
Jul 23 17:04:30 PC1 postfix/smtpd[26342]: SSL_accept error from
localhost.localdomain[127.0.0.1]: -1
Jul 23 17:04:30 PC1 postfix/smtp[26341]: SSL_connect error to
127.0.0.1[127.0.0.1]:12027: -1
Jul 23 17:04:30 PC1 postfix/smtp[26341]: remove session
dksign:127.0.0.1:12027:my.domain.tld&p=1&c=ALL:+RC4:@STRENGTH from client
cache
Jul 23 17:04:30 PC1 postfix/smtpd[26342]: lost connection after STARTTLS
from localhost.localdomain[127.0.0.1]
Jul 23 17:04:30 PC1 postfix/tlsmgr[26264]: delete smtp session
id=dksign:127.0.0.1:12027:my.domain.tld&p=1&c=ALL:+RC4:@STRENGTH
Jul 23 17:04:30 PC1 postfix/smtpd[26342]: disconnect from
localhost.localdomain[127.0.0.1]
Jul 23 17:04:30 PC1 postfix/smtp[26341]: 1AB4128411E: Cannot start TLS:
handshake failure
Jul 23 17:04:30 PC1 postfix/smtpd[26342]: connect from
localhost.localdomain[127.0.0.1]
Jul 23 17:04:30 PC1 postfix/smtp[26341]: discarding EHLO keywords: 8BITMIME
Jul 23 17:04:30 PC1 postfix/smtpd[26342]: 00F97284157:
client=dns.name.tld[xxx.xxx.xxx.xxx]
Jul 23 17:04:30 PC1 dkimproxy.out[24830]: DKIM signing - signed;
message-id=<51ee9b3a.9040...@my.domain.tld>, signer=<m...@my.domain.tld>,
from=<m...@my.domain.tld>
Jul 23 17:04:30 PC1 postfix/cleanup[26340]: 00F97284157:
message-id=<51ee9b3a.9040...@my.domain.tld>
Jul 23 17:04:30 PC1 postfix/qmgr[26257]: 00F97284157:
from=<m...@my.domain.tld>, size=1676, nrcpt=1 (queue active)
Jul 23 17:04:30 PC1 postfix/smtp[26341]: 1AB4128411E:
to=<m...@my.domain2.tld>, relay=127.0.0.1[127.0.0.1]:12027, delay=63,
delays=2.7/0.01/60/0.09, dsn=2.0.0, status=sent (250 2.0.0 Ok: queued as
00F97284157)
Jul 23 17:04:30 PC1 postfix/smtpd[26342]: disconnect from
localhost.localdomain[127.0.0.1]
Jul 23 17:04:30 PC1 postfix/qmgr[26257]: 1AB4128411E: removed
Jul 23 17:04:30 PC1 postfix/smtp[26343]: initializing the client-side TLS
engine
Jul 23 17:04:30 PC1 postfix/smtp[26343]: 00F97284157:
to=<m...@my.domain2.tld>, relay=mx0.ovh.net[xxx.xxx.xxx.xxx]:25, delay=0.28,
delays=0.09/0.02/0.07/0.11, dsn=2.0.0, status=sent (250 ok 1374591870 qp
8665)
Jul 23 17:04:30 PC1 postfix/qmgr[26257]: 00F97284157: removed




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