JP7226492B2 - Compound, active energy ray-curable coating composition, release coating composition, laminate, and method for producing laminate - Google Patents

Description

TECHNICAL FIELD The present disclosure relates to a compound, an active energy ray-curable coating composition, a release coating composition, a laminate, and a method for producing a laminate.

By adding compounds containing polysiloxane to resins, etc., high hardness, flexibility, heat resistance, weather resistance, impact resistance, crack resistance, abrasion resistance, corrosion resistance, water resistance, water repellency, electrical It is possible to obtain a cured product having properties such as insulating properties and workability. For this reason, compounds containing polysiloxane are used in various fields such as adhesives, self-healing coating agents, and release coating agents. When a compound containing polysiloxane is used in applications such as adhesives, self-healing coating agents, and release coating agents, the component bleeds out on the surface of the coating film, and the adhesive and the adhesive further laminated on the coating film. A compound containing polysiloxane may migrate to an adherend such as a resin molded article, and its properties may be impaired.

The problem to be solved in the present disclosure is a compound, an active energy ray-curable coating composition containing the compound, a release coating composition, a laminate thereof, and the production of a laminate, which satisfactorily suppresses migration of silicone. to provide a method.

As a result of extensive studies, the inventors have found that the above problems can be solved by using a given compound.

（一般式（１）中、
Ｘ_１～Ｘ_２、Ｘ_５～Ｘ_６は、それぞれ独立に、炭素数１以上４以下のアルキル基であり、
Ｘ_３～Ｘ_４は、それぞれ独立に、炭素数１以上４以下のアルキル基であり、繰返し単位毎に同一であっても異なっていてもよく、
ｎは、１以上４００以下の整数であり、
Ｙ_１及びＹ_２は、それぞれ独立に、
（Ｉ）エーテル結合を有していてもよい炭素数１以上２０以下の炭化水素基（Ｉ－Ｉ）と結合Ａ及び結合Ｂを含む構造（Ｉ－ＩＩ）と重合性不飽和基（Ｉ－ＩＩＩ）とをこの順番で含む構造、又は
（ＩＩ）エーテル結合を有していてもよい炭素数１以上２０以下の炭化水素基（ＩＩ－Ｉ）、結合Ａ又は結合Ｂを含む構造（ＩＩ－ＩＩ）及び重合性不飽和基（ＩＩ－ＩＩＩ）からなる群から選択される１種以上を含む構造であり、
Ｙ_１及びＹ_２のうち少なくとも一方が（Ｉ）であり、
Ｙ_１及びＹ_２の有する重合性不飽和基の合計数が４個以上であり、
結合Ａが構造式（１）～（３）から選択される一種以上の結合であり、
構造式（１）が

であり、
構造式（２）が

であり、
構造式（３）が

であり、
結合Ｂがウレタン結合である。）
（項目２）
（ａ－３）成分中のイソシアネート基の数が１個である、項目１に記載の化合物（ａ）。
（項目３）
（ａ－２）成分が、２－メルカプトエタノール、３－メルカプト－３－メチル－１－ブタノール、１－メルカプト－２－プロパノール、３－メルカプト－１－プロパノール及び１－チオグリセロールからなる群から選択される１種以上又はジエタノールアミン、２－ピペリジンメタノール、２－ピペリジンエタノール、３－ピペリジンメタノール、３－ピペリジンエタノール、４－ピペリジンメタノール、４－ピペリジンエタノール、２－ピペリジノール、３－ピペリジノール及び４－ピペリジノールからなる群から選択される１種以上であり、
（ａ－３）成分が、２－（メタ）アクリロイルオキシエチルイソシアネート、２－（２－メタクリロイルオキシエチルオキシ）エチルイソシアナート及び１，１－（ビス（メタ）アクリロイルオキシメチル）エチルイソシアネートからなる群から選択される１種以上である、項目１又は２に記載の化合物（ａ）。
（項目４）
項目１～３のいずれかに記載の化合物（ａ）、
２個以上の（メタ）アクリロイル基を含む成分（ｂ）、及び
光重合開始剤（ｃ）
を含む活性エネルギー線硬化型コーティング剤組成物。
（項目５）
項目４に記載の活性エネルギー線硬化型コーティング剤組成物を含む離型コーティング剤組成物。
（項目６）
基材と項目４に記載の活性エネルギー線硬化型コーティング剤組成物の硬化物又は項目５に記載の離型コーティング剤組成物の硬化物とを含む積層体。
（項目７）
基材の少なくとも片面に塗工した項目４に記載の活性エネルギー線硬化型コーティング剤組成物又は項目５に記載の離型コーティング剤組成物を、活性エネルギー線で硬化する工程を含む、積層体の製造方法。 The following items are provided by this disclosure.
(Item 1)
Component (a-1) containing a polymerizable unsaturated group and polysiloxane,
A component containing a thiol group and a hydroxyl group and / or a component containing an amino group and a hydroxyl group (a-2), and a component containing an isocyanate group and a polymerizable unsaturated group (a-3)
Compound (a) according to general formula (1), which is a reactant of a component containing
General formula (1):

(In general formula (1),
X ₁ to X ₂ and X ₅ to X ₆ are each independently an alkyl group having 1 to 4 carbon atoms,
X ₃ to X ₄ are each independently an alkyl group having 1 to 4 carbon atoms, and each repeating unit may be the same or different;
n is an integer of 1 or more and 400 or less,
Y ₁ and Y ₂ are each independently
(I) a hydrocarbon group (II) having 1 to 20 carbon atoms which may have an ether bond, a structure (I-II) containing a bond A and a bond B, and a polymerizable unsaturated group (I- III) in this order, or (II) a hydrocarbon group having 1 to 20 carbon atoms optionally having an ether bond (II-I), a structure containing a bond A or a bond B (II- II) and a structure containing one or more selected from the group consisting of polymerizable unsaturated groups (II-III),
at least one of Y ₁ and Y ₂ is (I);
Y ₁ and Y ₂ have a total number of polymerizable unsaturated groups of 4 or more,
bond A is one or more bonds selected from structural formulas (1) to (3);
Structural formula (1) is

and
Structural formula (2) is

and
Structural formula (3) is

and
Bond B is a urethane bond. )
(Item 2)
The compound (a) according to item 1, wherein the number of isocyanate groups in component (a-3) is one.
(Item 3)
Component (a-2) is selected from the group consisting of 2-mercaptoethanol, 3-mercapto-3-methyl-1-butanol, 1-mercapto-2-propanol, 3-mercapto-1-propanol and 1-thioglycerol or from diethanolamine, 2-piperidinemethanol, 2-piperidineethanol, 3-piperidinemethanol, 3-piperidineethanol, 4-piperidinemethanol, 4-piperidineethanol, 2-piperidinol, 3-piperidinol and 4-piperidinol One or more selected from the group consisting of
The group in which component (a-3) consists of 2-(meth)acryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate 3. The compound (a) according to item 1 or 2, which is one or more selected from
(Item 4)
the compound (a) according to any one of items 1 to 3,
Component (b) containing two or more (meth)acryloyl groups, and photoinitiator (c)
An active energy ray-curable coating composition comprising:
(Item 5)
A release coating composition comprising the active energy ray-curable coating composition according to Item 4.
(Item 6)
A laminate comprising a substrate and a cured product of the active energy ray-curable coating composition according to Item 4 or a cured product of the release coating composition according to Item 5.
(Item 7)
A laminate comprising a step of curing with an active energy ray the active energy ray-curable coating composition according to item 4 or the release coating composition according to item 5 applied to at least one side of a substrate. Production method.

The compounds provided by the present disclosure can effectively suppress silicone migration.

Throughout the present disclosure, the range of numerical values for each physical property value, content, etc. can be set as appropriate (for example, by selecting from the upper and lower limit values described in each item below). Specifically, regarding the numerical value φ, when the lower limit of the numerical value φ is A1, A2, A3, etc., and the upper limit of the numerical value φ is B1, B2, B3, etc., the range of the numerical value φ is A1 or more, A2 or more, A3 or more, B1 or less, B2 or less, B3 or less, A1-B1, A1-B2, A1-B3, A2-B1, A2-B2, A2-B3, A3-B1, A3-B2, A3-B3 etc. are exemplified. In the present disclosure, "~" is used to mean including the numerical values before and after it as lower and upper limits.

Compound (a) (also referred to as "(a) component" in the present disclosure) is a component (a-1) containing a polymerizable unsaturated group and polysiloxane ("(a-1) component" in the present disclosure) Also called.), a component containing a thiol group and a hydroxyl group and / or a component (a-2) containing an amino group and a hydroxyl group (also referred to as "(a-2) component" in the present disclosure), and an isocyanate group and polymerization It can be obtained by reacting a component containing a component (a-3) containing a polyunsaturated group (also referred to as “(a-3) component” in the present disclosure). The compound (a) thus obtained has a structure containing polysiloxane, a structure containing bond A and bond B, and a structure containing a polymerizable unsaturated group.

<(a-1) Component>
Component (a-1) is a component containing a polymerizable unsaturated group and polysiloxane. In the present disclosure, polysiloxane is represented by - silicon (Si) - oxygen (O) - [- silicon (Si) - oxygen (O) -] _L - silicon (Si) - (L is 1 or more.) It is a structure that Examples of polymerizable unsaturated groups include structures containing carbon-carbon double bonds and structures containing carbon-carbon triple bonds. Specific examples of polymerizable unsaturated groups include vinyl groups and (meth)acryloyl groups. As component (a-1), those represented by general formula (2) are exemplified.

（一般式（２）中、
χ_１～χ_２、χ_５～χ_６は、それぞれ独立に、炭素数１以上４以下のアルキル基であり、
χ_３～χ_４は、それぞれ独立に、炭素数１以上４以下のアルキル基であり、繰返し単位毎に同一であっても異なっていてもよく、
ψ_１～ψ_２は、それぞれ独立に、エーテル結合を有していてもよい炭素数１以上２０以下の直鎖状若しくは分岐状炭化水素基であり、
ｍは、１以上４００以下の整数であり、
ω_１～ω_４は、それぞれ独立に、水素原子又は重合性不飽和基である。） General formula (2):

(In general formula (2),
χ ₁ to χ ₂ and χ ₅ to χ ₆ are each independently an alkyl group having 1 to 4 carbon atoms,
χ ₃ to χ ₄ are each independently an alkyl group having 1 to 4 carbon atoms, and each repeating unit may be the same or different;
ψ ₁ to ψ ₂ are each independently a linear or branched hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond,
m is an integer of 1 or more and 400 or less,
ω ₁ to ω ₄ are each independently a hydrogen atom or a polymerizable unsaturated group. )

The upper limit of the number of carbon atoms of χ ₁ to χ ₆ in general formula (2) is exemplified as 4, 3, 2, etc., and the lower limit is exemplified as 3, 2, 1, etc., independently. In one embodiment, the number of carbon atoms in χ ₁ to χ ₆ in general formula (2) is preferably approximately 1 to 4 independently. The alkyl group having 1 to 4 carbon atoms of χ ₁ to χ ₆ in the general formula (2) is a methyl group, an ethyl group, a propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, an isobutyl group, or a secondary A butyl group is exemplified. That is, the alkyl groups of χ ₁ to χ ₆ and having 1 to 4 carbon atoms may be linear or branched.

The “linear or branched hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond” for ψ ₁ and ψ ₂ in the general formula (2) means It refers to a linear hydrocarbon group having 1 or more and 20 or less carbon atoms or a branched hydrocarbon group having 1 or more and 20 or less carbon atoms which may have an ether bond. The upper limit of the number of carbon atoms of ψ ₁ and ψ ₂ in general formula (2) is independently exemplified by 20, 18, 16, 14, 12, 10, 8, 6, 4, 2, etc., and the lower limit is 18. , 16, 14, 12, 10, 8, 6, 4, 2, 1, and the like. In one embodiment, the number of carbon atoms in ψ ₁ and ψ ₂ in general formula (2) is preferably approximately 1 or more and 20 or less. C _α H _2α-1 (where α is an integer of 1 or more and 20 or less) as linear or branched hydrocarbon groups having 1 or more and 20 or less carbon atoms in ψ ₁ and ψ ₂ of general formula (2). A structure represented by is exemplified. Moreover, it may have an ester bond in addition to the ether bond.

The upper limit of m in the general formula (2) is 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 75, 50, 25, 10, 5, 3, 1, etc. are exemplified as lower limits. In one embodiment, m in general formula (2) is an integer of 1 or more and 400 or less.

At least one of ω ₁ to ω ₄ in formula (2) is a polymerizable unsaturated group. Among ω ₁ to ω ₄ , the number of polymerizable unsaturated groups is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or more and 2 or less. is.

Specific examples of the component (a-1) represented by the general formula (2) include components containing (meth)acryloyl groups at both ends of polysiloxane (product names “X-22-164”, “X-22-164AS” , "X-22-164A", "X-22-164B", "X-22-164C", "X-22-164E" (manufactured by Shin-Etsu Chemical Co., Ltd.)), polysiloxane at one end (meth ) Components containing acryloyl groups (product names “X-22-174ASX”, “X-22-174BX”, “KF-2012”, “X-22-2426”, “X-22-2404” (Shin-Etsu Chemical Co., Ltd. Co., Ltd.) (product names “Silaplane FM-0711”, “Silaplane FM-0721”, “Silaplane FM-0725” (manufactured by JNC Corporation)) and the like.

Component (a-1-1) containing a reactive functional group (e.g., COOH group, etc.) and polysiloxane (also referred to as "(a-1-1) component" in the present disclosure) and its reactive functional group A reacting functional group (e.g., OH group, etc.) and a component (a-1-2) containing a polymerizable unsaturated group (also referred to as "(a-1-2) component" in the present disclosure) are reacted. Thus, it is also possible to obtain the component (a-1). Examples of reactive functional groups include -OH group, -COOH group, -COOCO- group, -NCO group, -SH group, epoxy group, oxazoline group, amino group and polymerizable unsaturated group. Examples of amino groups include primary amino groups (--NH ₂ ) and secondary amino groups (--NH--). The combination of reactive functional groups in the components (a-1-1) and (a-1-2) includes —OH group and —COOH group, amino group and polymerizable unsaturated group, —SH group and polymerizable unsaturated group. Examples include saturated groups, -OH groups and -NCO groups, amino groups and -NCO groups, -OH groups and -COOCO- groups, and the like.

Component (a-1-1) is exemplified by those in which at least one of ω ₁ to ω ₄ in general formula (2) is the above reactive functional group. The component (a-1-1) may be a commercially available product. As such products, polysiloxane components containing amino groups at both ends (product names “X-22-161A”, “X-22-161B”, “KF-8012”, “KF-8008” (Shin-Etsu Chemical Co., Ltd. )), polysiloxane components containing epoxy groups at both ends (product names “X-22-163”, “X-22-163A”, “X-22-163B”, “X-22-163C” ( Shin-Etsu Chemical Co., Ltd.)), components containing —OH groups at both ends of polysiloxane (product names “KF-6000”, “KF-6001”, “KF-6002”, “KF-6003” (Shin-Etsu Chemical Kogyo Co., Ltd.), product names "Silaplane FM-4411", "Silaplane FM-4421", "Silaplane FM-4425" (manufactured by JNC Co., Ltd.), -SH groups at both ends of polysiloxane Components containing (product names “X-22-167B”, “X-22-167C” (manufactured by Shin-Etsu Chemical Co., Ltd.)), components containing —COOH groups at both ends of polysiloxane (product name “X-22- 162C” (manufactured by Shin-Etsu Chemical Co., Ltd.), polysiloxane component containing an epoxy group at one end (product names “X-22-173BX”, “X-22-173DX” (manufactured by Shin-Etsu Chemical Co., Ltd.) ), components containing —OH groups at one end of polysiloxane (product names “X-22-170BX”, “X-22-170DX”, “X-22-176DX”, “X-22-176F”, “X -22-176GX-A” (manufactured by Shin-Etsu Chemical Co., Ltd.) (product names “Silaplane FM-0411”, “Silaplane FM-0421”, “Silaplane FM-0425”, “Silaplane FM-DA11” ”, “Silaplane FM-DA21”, “Silaplane FM-DA26” (manufactured by JNC Co., Ltd.), a component containing a —COOH group at one end of polysiloxane (product name “X-22-3710” (Shin-Etsu Chemical Kogyo Co., Ltd.), components containing (meth)acryloyl groups at both polysiloxane ends (product names “X-22-164”, “X-22-164AS”, “X-22-164A”, “X -22-164B", "X-22-164C", "X-22-164E" (manufactured by Shin-Etsu Chemical Co., Ltd.)) Product names "Silaplane FM-7711", "Silaplane FM-7721", " Silaplane FM-7725” (manufactured by JNC Co., Ltd.), a polysiloxane component containing a (meth)acryloyl group at one end (product names “X-22-174ASX”, “X-22-174BX” , “KF-2012”, “X-22-2426”, “X-22-2404” (manufactured by Shin-Etsu Chemical Co., Ltd.)) (product names “Silaplane FM-0711”, “Silaplane FM-0721” , “Silaplane FM-0725” (manufactured by JNC Corporation), and the like.

The substances exemplified as component (a-1-1) and known substances as component (a-1-1) can be used alone or in combination of two or more. Component (a-1-1) is preferably a component containing OH groups and polysiloxane and/or a component containing amino groups and polysiloxane.

The upper limit of the number average molecular weight of component (a-1-1) is 000, 18,500, 18,000, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000, 14,500, 14,000, 13,500, 13,000, 12,500, 12,000, 11,500, 11,000, 10,500, 10,000, 9,500, 9,000, 8,500, 8,000, 7,500, 7,000, 6, 500, 6,000, 5,500, 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, etc., and the lower limit is 45, 000, 40,000, 35,000, 30,000, 25,000, 20,000, 19,500, 19,000, 18,500, 18,000, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000, 14,500, 14,000, 13,500, 13,000, 12,500, 12,000, 11,500, 11,000, 10,500, 10, 000, 9,500, 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, 1,000 and the like are exemplified. In one embodiment, the number average molecular weight of component (a-1-1) is preferably about 1,000 to 20,000. If the number average molecular weight of the component (a-1-1) is at least the above lower limit, it is considered that the composition containing the compound (a) of the present disclosure tends to be excellent in easy peelability when used as a release layer. there is It is believed that the higher the number average molecular weight of the component (a-1-1), the better the easy peelability tends to be. On the other hand, we believe that the lower the number average molecular weight of the component (a-1-1), the better the suppression of silicone transfer. In the present disclosure, the number average molecular weight is a polystyrene-equivalent value obtained by gel permeation chromatography.

The upper limit of the functional group equivalent (g/mol) of component (a-1-1) is 50,000, 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 19 , 500, 19,000, 18,500, 18,000, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000, 14,500, 14,000, 13,500 , 13,000, 12,500, 12,000, 11,500, 11,000, 10,500, 10,000, 9,500, 9,000, 8,500, 8,000, 7,500, 7 , 000, 6,500, 6,000, 5,500, 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, etc. , the lower limit is 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 19,500, 19,000, 18,500, 18,000, 17,500, 17,000 , 16,500, 16,000, 15,500, 15,000, 14,500, 14,000, 13,500, 13,000, 12,500, 12,000, 11,500, 11,000, 10 , 500, 10,000, 9,500, 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, 5,000, 4,500 , 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, 1,000, and the like. In one embodiment, the functional group equivalent (g/mol) of component (a-1-1) is preferably about 1,000 to 20,000. If the functional group equivalent (g/mol) of the component (a-1-1) is at least the above lower limit, the composition containing the compound (a) of the present disclosure tends to be excellent in easy peelability when used as a release layer. I think it's in It is believed that the higher the functional group equivalent (g/mol) of the component (a-1-1), the better the easy peelability tends to be. On the other hand, it is believed that the lower the functional group equivalent (g/mol) of the component (a-1-1), the better the suppression of silicone transfer. In addition, in this disclosure, the functional group equivalent is the molecular weight per functional group.

The upper limit of the content (in terms of solid content) of component (a-1-1) in the total 100 mass% (in terms of solid content) of the components constituting component (a-1) is 99, 98, 97, 96, 95, 94, 93, 92, 91, 90, 85, 80, 75, 70, 65, 60, 55% by mass, etc., and the lower limits are 98, 97, 96, 95, 94, 93, 92, 91 , 90, 85, 80, 75, 70, 65, 60, 55, 50% by mass, and the like. In one embodiment, the content of component (a-1-1) in the total 100% by mass (in terms of solid content) of components constituting component (a-1) (in terms of solid content) is 50 to 99 mass. % is preferred.

(a-1-2) as a component, a component containing a -OH group and a polymerizable unsaturated group, a component containing a -COOH group and a polymerizable unsaturated group, a component containing a -COOCO- group and a polymerizable unsaturated group, a component containing a -NCO group and a polymerizable unsaturated group, a component containing a -SH group and a polymerizable unsaturated group, a component containing an epoxy group and a polymerizable unsaturated group, a component containing an oxazoline group and a polymerizable unsaturated group, Components containing an amino group and a polymerizable unsaturated group are exemplified. -OH group and a polymerizable unsaturated group-containing component, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, (meth) ) 2-hydroxy-3-phenoxypropyl acrylate, glycerin di(meth)acrylate, 2-hydroxy-3-(meth)acryloyl-oxypropyl(meth)acrylate, 1-((meth)acryloyloxy)-3-( (Meth)acryloyloxy-2-propanol, pentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, tripentaerythritol hepta(meth)acrylate, etc. —COOH group and the component containing a polymerizable unsaturated group, (meth) acrylic acid, 2-(meth) acryloyloxyethyl phthalic acid, mono succinate (2-(meth) acryloyloxyethyl), etc. are exemplified.-COOCO Examples of components containing a - group and a polymerizable unsaturated group include (meth)acrylic anhydride, crotonic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, etc. -NCO group and polymerizable unsaturated group Allyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, etc. Examples of the component containing an epoxy group and a polymerizable unsaturated group include (3,4-epoxycyclohexyl)methyl (meth)acrylate, glycidyl (meth)acrylate, allyl glycidyl ether, etc. Oxazoline Examples of components containing a group and a polymerizable unsaturated group include 2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline-5-one, 2-vinyl-2-oxazoline, and the like. Components containing an amino group and a polymerizable unsaturated group include 3-amino-1-propene, 3-amino-2-methyl-1-propene, 2-(2-propynyloxy)ethylamine, diallylamine, di(2 -propynyl)amine, 1,1-dimethyl-2-propynylamine, aminophenylacetylene, vinylaniline, N-tert-butylallylamine, oleylamine and the like.

A commercially available product may be used as the component (a-1-2). As such products, 2-hydroxyethyl (meth)acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 4-hydroxybutyl (meth)acrylate (manufactured by Mitsubishi Chemical Corporation), 3-hydroxy-1-(meth)acrylic acid Adamantyl (manufactured by Tokyo Chemical Industry Co., Ltd.), 2-hydroxy-3-phenoxypropyl (meth)acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2-(meth) acryloyloxyethyl phthalate (Shin-Nakamura Chemical Industry Co., Ltd.) Co., Ltd.), succinic acid mono(2-(meth)acryloyloxyethyl) (manufactured by Tokyo Chemical Industry Co., Ltd.), 1,1-(bisacryloyloxymethyl)ethyl isocyanate (product name “Karenzu BEI”, Showa Denko Co., Ltd.), 2-acryloyloxyethyl isocyanate (product name “Karenzu AOI”, Showa Denko Co., Ltd.), 2-hydroxy-3-acryloyl-oxypropyl (meth)acrylate (product name “Blemmer GAM ”, “Blenmer GAM-R” manufactured by NOF Corporation), and diallylamine (manufactured by Tokyo Chemical Industry Co., Ltd.).

The substances exemplified as component (a-1-2) and those known as component (a-1-2) can be used alone or in combination of two or more. Component (a-1-2) is preferably a component containing a -COOCO- group and a polymerizable unsaturated group and/or a component containing a -NCO group and a polymerizable unsaturated group, more preferably anhydrous (meth) One selected from acrylic acid, crotonic anhydride, maleic anhydride, itaconic anhydride and citraconic anhydride and/or allyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxy One selected from ethyloxyethyl isocyanate and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, more preferably one selected from maleic anhydride, itaconic anhydride and citraconic anhydride and/or 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxyethyl isocyanate and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate) and particularly preferably maleic anhydride, 2-(meth)acryloyloxyethyl isocyanate, and/or 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate.

The upper limit of the molecular weight of component (a-1-2) is 150, 100, etc. are exemplified, and the lower limits are exemplified. In one embodiment, the molecular weight of component (a-1-2) is preferably about 50 to 1,000. In the present disclosure, the term "molecular weight" simply refers to a numerical value calculated on the basis of atomic weight.

The upper limit of the number of carbon atoms in component (a-1-2) is exemplified by 100, 90, 80, 70, 60, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, etc. Examples of lower limits include 90, 80, 70, 60, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 3, and the like. In one embodiment, the number of carbon atoms in component (a-1-2) is preferably about 3 to 100.

The upper limit of the mass ratio of the solid content of the component (a-1-1) and the component (a-1-2) (component (a-1-1)/component (a-1-2)) is 99/1, 98/2, 97/3, 96/4, 95/5, 94/6, 93/7, 92/8, 91/9, 90/10, 80/20, 70/30, 60/40 are exemplified. , the lower limits are 99/1, 98/2, 97/3, 96/4, 95/5, 94/6, 93/7, 92/8, 91/9, 90/10, 80/20, 70/ 30, 60/40, 50/50 and the like are exemplified. In one embodiment, the mass ratio of the solid content of component (a-1-1) and component (a-1-2) ((a-1-1) component/(a-1-2) component) is About 50/50 to 99/1 is preferable.

The upper limit of the content (in terms of solid content) of component (a-1-2) in the total 100% by mass (in terms of solid content) of the components constituting component (a-1) is 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2% by mass, etc., and the lower limit is 45, 40, 35, 30, 25, 20, 15, 10 , 9, 8, 7, 6, 5, 4, 3, 2, 1% by mass, and the like. In one embodiment, the content (in terms of solid content) of component (a-1-2) in the total 100% by mass (in terms of solid content) of components constituting component (a-1) is 1 to 50 mass. % is preferred.

The substances exemplified as component (a-1) and those known as component (a-1) can be used alone or in combination of two or more.

The upper limit of the number average molecular weight of component (a-1) is 18,500, 18,000, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000, 14,500, 14,000, 13,500, 13,000, 12, 500, 12,000, 11,500, 11,000, 10,500, 10,000, 9,500, 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, etc., and the lower limit is 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 19,500, 19,000, 18,500, 18,000, 17,500, 17,000, 16,500, 16, 000,15,500,15,000,14,500,14,000,13,500,13,000,12,500,12,000,11,500,11,000,10,500,10,000, 9,500, 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, 5,000, 4,500, 4,000, 3, 500, 3,000, 2,500, 2,000, 1,500, 1,000 and the like are exemplified. In one embodiment, the number average molecular weight of component (a-1) is preferably about 1,000 to 20,000. If the number average molecular weight of the component (a-1) is at least the above lower limit, it is believed that the composition containing the compound (a) of the present disclosure tends to be excellent in light release properties when used as a release layer. It is believed that the higher the number average molecular weight of the component (a-1), the better the easy peelability tends to be. On the other hand, it is believed that the lower the number average molecular weight of the component (a-1), the better the suppression of silicone transfer. In the present disclosure, the number average molecular weight is a polystyrene-equivalent value obtained by gel permeation chromatography.

The upper limit of the functional group equivalent (g/mol) of component (a-1) is 50,000, 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 19,500 , 19,000, 18,500, 18,000, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000, 14,500, 14,000, 13,500, 13 ,000, 12,500, 12,000, 11,500, 11,000, 10,500, 10,000, 9,500, 9,000, 8,500, 8,000, 7,500, 7,000 , 6,500, 6,000, 5,500, 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, etc., and the lower limit is 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 19,500, 19,000, 18,500, 18,000, 17,500, 17,000, 16 , 500, 16,000, 15,500, 15,000, 14,500, 14,000, 13,500, 13,000, 12,500, 12,000, 11,500, 11,000, 10,500 , 10,000, 9,500, 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, 5,000, 4,500, 4 ,000, 3,500, 3,000, 2,500, 2,000, 1,500, 1,000 and the like are exemplified. In one embodiment, the functional group equivalent (g/mol) of component (a-1) is preferably about 1,000 to 20,000. If the functional group equivalent (g/mol) of the component (a-1) is at least the above lower limit, the composition containing the compound (a) of the present disclosure tends to be easily peeled when used as a peeling layer. I believe. It is believed that the higher the functional group equivalent (g/mol) of the component (a-1), the better the easy peelability tends to be. On the other hand, it is believed that the lower the functional group equivalent (g/mol) of the component (a-1), the better the suppression of silicone transfer. In addition, in this disclosure, the functional group equivalent is the molecular weight per functional group. Moreover, the polymerizable unsaturated group, which is the functional group of the component (a-1), may be at both ends or at one end of the polysiloxane chain.

The upper limit of the number of polymerizable unsaturated groups in component (a-1) is exemplified by 20, 15, 10, 8, 6, 4, 2, etc., and the lower limit is 15, 10, 8, 6, 4. , 2, 1, etc. are exemplified. In one embodiment, the number of polymerizable unsaturated groups in component (a-1) is preferably about 1 to 20.

The upper limit of the content (in terms of solid content) of component (a-1) in the total 100 mass% (in terms of solid content) of the components constituting compound (a) is 98, 95, 90, 85, 80, 75, 70, 65, 60, 55% by mass, etc. are exemplified, and the lower limit is exemplified by 95, 90, 85, 80, 75, 70, 65, 60, 55, 50% by mass. In one embodiment, the content (in terms of solid content) of component (a-1) in the total 100% by mass (in terms of solid content) of the components constituting compound (a) is preferably about 50 to 98% by mass. . It is considered that the greater the content of component (a-1) in the total 100% by mass (in terms of solid content) of the components constituting compound (a), the better the easy peelability tends to be. On the other hand, the smaller the content of component (a-1) in the total 100% by mass (in terms of solid content) of the components constituting compound (a), the better the silicone migration can be suppressed, and the better the compatibility. I think there is a tendency to

<(a-2) component>
Component (a-2) is a component containing a thiol group and a hydroxyl group and/or a component containing an amino group and a hydroxyl group. The shape of the component (a-2) is exemplified by a linear shape, a branched shape, and the like.

Components containing a thiol group and a hydroxyl group include 2-mercaptoethanol, 3-mercapto-3-methyl-1-butanol, 1-mercapto-2-propanol, 3-mercapto-1-propanol, 2-hydroxybenzenethiol, 4- Mercaptophenol, 2-mercaptohydroquinone, 11-mercaptoundecylhydroquinone, 2,3-dimercaptopropanol, 1-thioglycerol, dithiothreitol and the like are examples. A component containing a thiol group and a hydroxyl group may be synthesized by various known methods. A method for synthesizing a component containing a thiol group and a hydroxyl group is exemplified by the reaction of hydrogen sulfide (H ₂ S) with an epoxide. Epoxides include 1-butoxy-2,3-epoxypropane, 1,2-epoxybutane, 1-tert-butoxy-2,3-epoxypropane, 1-dodecene epoxide, 1,2-octylene oxide, 1, Examples include 2-pentylene oxide and cyclopentene oxide.

Components containing an amino group and a hydroxyl group include ethanolamine, diethanolamine, ethylethanolamine, propanolamine, 4-amino-1-butanol, 2-aminobutyl alcohol, 5-amino-1-pentanol, 6-amino-1- Hexanol, 8-amino-1-octanol, 10-amino-1-decanol, 12-amino-1-dodecanol, 3-amino-1-propanol, 1-aminopropan-2-ol, 3-amino-1,2 -propanediol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, iminodipropanol, 2 -[(hydroxymethyl)amino]ethanol, 2,2'-dihydroxydiethylamine, 3-methylamino-1,2-propanediol, 2-hydroxy-1,3-diaminopropane, 2-amino-2-hydroxymethyl- 1,3-propanediol, 2-piperidinemethanol, 2-piperidineethanol, 3-piperidinemethanol, 3-piperidineethanol, 4-piperidinemethanol, 4-piperidineethanol, 2-piperidinol, 3-piperidinol, 4-piperidinol, etc. exemplified.

Substances exemplified as component (a-2) and known substances as component (a-2) can be used alone or in combination of two or more. Component (a-2) is preferably a component containing a thiol group and a hydroxyl group or a component containing an amino group and a hydroxyl group, more preferably 2-mercaptoethanol, 3-mercapto-3-methyl-1-butanol, 1- One or more selected from the group consisting of mercapto-2-propanol, 3-mercapto-1-propanol and 1-thioglycerol, or diethanolamine, 2-piperidinemethanol, 2-piperidineethanol, 3-piperidinemethanol, 3-piperidineethanol , 4-piperidinemethanol, 4-piperidineethanol, 2-piperidinol, 3-piperidinol and 4-piperidinol, and particularly preferably 1-thioglycerol or diethanolamine. Since the solvent resistance is particularly good, a component (a-2) containing a thiol group and a hydroxyl group is better than a component containing an amino group and a hydroxyl group.

The upper limit of the molecular weight of component (a-2) is 500, 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 75, 50, etc. are exemplified, and the lower limits are exemplified by 475, 450, 425, 400, 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 75, 50, 25 and the like. In one embodiment, the molecular weight of component (a-2) is preferably about 25-500.

The upper limit of the number of carbon atoms in component (a-2) is 50, 40, 30, 28, 26, 24, 22, 20, 18, 16, 15, 14, 12, 10, 8, 6, 4, 2, etc. are exemplified, and the lower limits are exemplified by 40, 30, 28, 26, 24, 22, 20, 18, 16, 15, 14, 12, 10, 8, 6, 4, 2, 1, and the like. In one embodiment, the number of carbon atoms in component (a-2) is preferably about 1 to 15.

The upper limit of the number of hydroxyl groups in component (a-2) is exemplified by 10, 9, 8, 7, 6, 5, 4, 3, 2, etc., and the lower limit is 9, 8, 7, 6, 5. , 4, 3, 2, 1, etc. are exemplified. In one embodiment, the number of hydroxyl groups in component (a-2) is preferably about 1 to 10. The upper limit of the number of thiol groups or amino groups in component (a-2) is exemplified by 10, 9, 8, 7, 6, 5, 4, 3, 2, etc., and the lower limit is 9, 8, 7. , 6, 5, 4, 3, 2, 1, and the like. In one embodiment, the number of thiol groups or amino groups in component (a-2) is preferably about 1 to 10. The number of thiol groups or amino groups in the component (a-2) is particularly preferably 1, since it facilitates peeling.

The upper limits of the mass ratio of the solid content of components (a-1) and (a-2) (component (a-1)/component (a-2)) are 99.5/0.5, 99/1, 98/2, 97/3, 96/4, 95/5, 94/6, 93/7, 92/8, 91/9, 90/10, 85/15, 80/20, etc., and the lower limit is , 99/1, 98/2, 97/3, 96/4, 95/5, 94/6, 93/7, 92/8, 91/9, 90/10, 85/15, 80/20, 75 /25 and the like are exemplified. In one embodiment, the mass ratio of the solid content of component (a-1) and component (a-2) ((a-1) component/(a-2) component) is 75/25 to 99.5/ About 0.5 is preferable.

The upper limit of the content (in terms of solid content) of component (a-2) in the total 100% by mass (in terms of solid content) of the components constituting compound (a) is 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1% by mass, etc. are exemplified, and the lower limits are 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5% by mass, etc. exemplified. In one embodiment, the content (in terms of solid content) of component (a-2) in the total 100% by mass (in terms of solid content) of the components constituting compound (a) is about 0.5 to 20% by mass. is preferred.

<(a-3) Component>
Component (a-3) is a component containing an isocyanate group and a polymerizable unsaturated group. The shape of the component (a-3) is exemplified by a straight chain, a branched chain, and the like.

(a-3) as component allyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-(bis(meth)acryloyloxy Methyl) ethyl isocyanate and the like are exemplified. Component (a-3) is a component (a-3-1) having two or more isocyanate groups, a functional group (e.g., OH group) that reacts with the isocyanate group, and a component (a-3) having a polymerizable unsaturated group. -2) may be obtained by reacting with. Examples of such component (a-3) include half urethanes of hexamethylene diisocyanate or isophorone diisocyanate and hydroxyethyl (meth)acrylate.

The substances exemplified as component (a-3) and those known as component (a-3) can be used alone or in combination of two or more. Component (a-3) is preferably 2-(meth)acryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate and 1,1-(bis One or more selected from the group consisting of (meth)acryloyloxymethyl)ethyl isocyanate, preferably 2-(meth)acryloyloxyethyl isocyanate and/or 1,1-(bis(meth)acryloyloxymethyl)ethyl is an isocyanate.

The upper limit of the molecular weight of component (a-3) is 100, etc. are exemplified, and the lower limits are exemplified by 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, etc. be. In one embodiment, the molecular weight of component (a-3) is preferably about 50 to 1,000.

The upper limit of the number of carbon atoms in component (a-3) is 100, 90, 80, 70, 60, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, etc. , 90, 80, 70, 60, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 3, and the like. In one embodiment, the number of carbon atoms in component (a-3) is preferably about 3 to 100.

The upper limit of the number of isocyanate groups in component (a-3) is exemplified by 10, 9, 8, 7, 6, 5, 4, 3, 2, etc., and the lower limit is 9, 8, 7, 6, 5, 4, 3, 2, 1, etc. are exemplified. In one embodiment, the number of isocyanate groups in component (a-3) is preferably about 1 to 10. The number of isocyanate groups in the component (a-3) is most preferably 1, since it facilitates peeling. The upper limit of the number of polymerizable unsaturated groups in component (a-3) is exemplified by 10, 9, 8, 7, 6, 5, 4, 3, 2, etc., and the lower limit is 9, 8, 7. , 6, 5, 4, 3, 2, 1, and the like. In one embodiment, the number of polymerizable unsaturated groups in component (a-3) is preferably about 1 to 10.

The upper limits of the mass ratio of the solid content of components (a-1) and (a-3) (component (a-1)/component (a-3)) are 99/1, 95/5, 90/10, Examples include 85/15, 80/20, 75/25, etc., and the lower limits include 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, and the like. In one embodiment, the mass ratio of the solid content of component (a-1) and component (a-3) ((a-1) component/(a-3) component) is about 70/30 to 99/1 is preferred.

The upper limits of the mass ratio of the solid content of components (a-2) and (a-3) (component (a-2)/component (a-3)) are 40/60, 35/65, 30/70, 25/75, 20/80, 15/85, 10/90, etc. are exemplified, and the lower limits are 35/65, 30/70, 25/75, 20/80, 15/85, 10/90, 5/95 etc. are exemplified. In one embodiment, the mass ratio of the solid content of component (a-2) and component (a-3) ((a-2) component/(a-3) component) is about 5/95 to 40/60 is preferred.

The upper limit of the content (in terms of solid content) of component (a-3) in the total 100 mass% (in terms of solid content) of the components constituting compound (a) is 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2% by mass, etc., and the lower limit is 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4 , 3, 2, 1% by mass, and the like. In one embodiment, the content (in terms of solid content) of component (a-3) in the total 100% by mass (in terms of solid content) of the components constituting compound (a) is preferably about 1 to 40% by mass. .

<Other ingredients>
A component (a-4) other than the components (a-1), (a-2), and (a-3) may be used as components constituting the compound (a). Examples of component (a-4) include components having functional groups that react with the functional groups of components (a-1), (a-2), and (a-3). Component (a-4) may be reacted with any one of components (a-1), (a-2) and (a-3). As the component (a-4), for example, when a component having a tri- or more functional isocyanate group is used, peeling tends to become difficult, so it is preferable not to use a component having a tri- or more functional isocyanate group. It is also possible to use component (a-4) as a component in synthesizing component (a-1), but for the same reason as above, components having tri- or higher functional isocyanate groups should not be used. is preferred. It is believed that this is due to the fact that the weight ratio of the polysiloxane portion is lower than when a component having less than trifunctional isocyanate groups is used due to the components having trifunctional or higher isocyanate groups. there is

<Compound (a)>
Compound (a) of the present disclosure has the structure of general formula (1).

（一般式（１）中、
Ｘ_１～Ｘ_２、Ｘ_５～Ｘ_６は、それぞれ独立に、炭素数１以上４以下のアルキル基であり、
Ｘ_３～Ｘ_４は、それぞれ独立に、炭素数１以上４以下のアルキル基であり、繰返し単位毎に同一であっても異なっていてもよく、
ｎは、１以上４００以下の整数であり、
Ｙ_１及びＹ_２は、それぞれ独立に、
（Ｉ）エーテル結合を有していてもよい炭素数１以上２０以下の炭化水素基（Ｉ－Ｉ）と結合Ａ及び結合Ｂを含む構造（Ｉ－ＩＩ）と重合性不飽和基（Ｉ－ＩＩＩ）とをこの順番で含む構造、又は
（ＩＩ）エーテル結合を有していてもよい炭素数１以上２０以下の炭化水素基（ＩＩ－Ｉ）、結合Ａ又は結合Ｂを含む構造（ＩＩ－ＩＩ）及び重合性不飽和基（ＩＩ－ＩＩＩ）からなる群から選択される１種以上を含む構造であり、
Ｙ_１及びＹ_２のうち少なくとも一方が（Ｉ）であり、
Ｙ_１及びＹ_２の有する重合性不飽和基の合計数が４個以上であり、
結合Ａが構造式（１）～（３）から選択される一種以上の結合であり、
構造式（１）が

であり、
構造式（２）が

であり、
構造式（３）が

であり、
結合Ｂがウレタン結合である。） General formula (1):

(In general formula (1),
X ₁ to X ₂ and X ₅ to X ₆ are each independently an alkyl group having 1 to 4 carbon atoms,
X ₃ to X ₄ are each independently an alkyl group having 1 to 4 carbon atoms, and each repeating unit may be the same or different;
n is an integer of 1 or more and 400 or less,
Y ₁ and Y ₂ are each independently
(I) a hydrocarbon group (II) having 1 to 20 carbon atoms which may have an ether bond, a structure (I-II) containing a bond A and a bond B, and a polymerizable unsaturated group (I- III) in this order, or (II) a hydrocarbon group having 1 to 20 carbon atoms optionally having an ether bond (II-I), a structure containing a bond A or a bond B (II- II) and a structure containing one or more selected from the group consisting of polymerizable unsaturated groups (II-III),
at least one of Y ₁ and Y ₂ is (I);
Y ₁ and Y ₂ have a total number of polymerizable unsaturated groups of 4 or more,
bond A is one or more bonds selected from structural formulas (1) to (3);
Structural formula (1) is

and
Structural formula (2) is

and
Structural formula (3) is

and
Bond B is a urethane bond. )

The upper limit of the number of carbon atoms of X ₁ to X ₆ in general formula (1) is exemplified as 4, 3, 2, etc., and the lower limit is exemplified as 3, 2, 1, etc., independently. In one embodiment, the number of carbon atoms of X ₁ to X ₆ in general formula (1) is preferably about 1 to 4 independently. The alkyl group having 1 to 4 carbon atoms of X ₁ to X ₆ in general formula (1) is a methyl group, an ethyl group, a propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, an isobutyl group, or a secondary A butyl group is exemplified. That is, the alkyl group having 1 to 4 carbon atoms of X ₁ to X ₆ may be linear or branched.

The upper limit of n in the general formula (1) is 375, 350, 325, 300, 275, 250, 225, 200, 175, 150, 125, 100, 75, 50, 25, 10, 5, 3, 1, etc. are exemplified as lower limits. In one embodiment, n in general formula (1) is an integer of 1 or more and 400 or less.

The “hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond” of Y ₁ and Y ₂ in the general formula (1) may be linear or branched. good. The upper limit of the number of carbon atoms in the “hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond” of Y ₁ and Y ₂ in the general formula (1) is independently 20, 18, 16, 14, 12, 10, 8, 6, 4, 2, etc. are exemplified, and the lower limit is exemplified as 18, 16, 14, 12, 10, 8, 6, 4, 2, 1, etc. In one embodiment, the number of carbon atoms in the "hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond" of Y ₁ and Y ₂ in general formula (1) is each independently 1 or more. About 20 or less is preferable. C _β H _{2β+1 ,} C β H _2β , or C _{β H 2β−1 (} β is , an integer of 1 or more and 20 or less). At least one of Y ₁ and Y ₂ in formula (1) is (I). Moreover, it may have an ester bond in addition to the ether bond.

The upper limit of the number of polymerizable unsaturated groups of Y ₁ and Y ₂ in the general formula (1) of the compound (a) is 64, 62, 60, 58, 56, 54, 52, 50, 48, 46, 44 , 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 22, 20, 18, 16, 14, 12, 10, 9, 8, 7, 6, 5, etc. are exemplified, Lower limits are 62, 60, 58, 56, 54, 52, 50, 48, 46, 44, 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 22, 20, 18, 16 , 14, 12, 10, 9, 8, 7, 6, 5, 4, and the like. In one embodiment, the number of polymerizable unsaturated groups possessed by Y ₁ and Y ₂ in general formula (1) of compound (a) is 4 or more, preferably about 4 to 64.

Y ₁ and / or Y ₂ in the general formula (1) of the compound (a) "a hydrocarbon group (II) having 1 to 20 carbon atoms which may have an ether bond, a bond A and a bond B and a polymerizable unsaturated group (I-III) in this order” means that “a structure that may have an ether bond in the order closest to the polysiloxane chain has 1 carbon number structure (I-II) containing 20 or less hydrocarbon groups (II), bond A and bond B, and polymerizable unsaturated group (I-III) in this order”. Y ₁ or Y ₂ of general formula (1) of compound (a) "hydrocarbon group (II-I) having 1 to 20 carbon atoms optionally having an ether bond, including bond A or bond B The structure containing one or more selected from the group consisting of structure (II-II) and polymerizable unsaturated group (II-III)" preferably means "one or more carbon atoms optionally having an ether bond 20 or less hydrocarbon group (II-I)", "a structure containing a hydrocarbon group (II-I) having 1 to 20 carbon atoms which may have an ether bond and a bond A or a bond B (II- Structure containing II)", "structure containing a hydrocarbon group (II-I) having 1 to 20 carbon atoms which may have an ether bond and a polymerizable unsaturated group (II-III)", "bond A or a structure containing a bond B (II-II) and a polymerizable unsaturated group (II-III)", or "a hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond (II-I) and a structure (II-II) containing a bond A or a bond B and a structure containing a polymerizable unsaturated group (II-III)", more preferably "having an ether bond A hydrocarbon group having 1 to 20 carbon atoms which may be present (II-I)”, “a hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond in order from the polysiloxane chain (II-I) -I) and a structure (II-II) containing a bond A or a bond B in that order", "In order closer to the polysiloxane chain, the A structure containing a hydrocarbon group (II-I) and a polymerizable unsaturated group (II-III) in this order", or "a structure containing a bond A or a bond B in the order closest to the polysiloxane chain (II-II) and a polymerizable unsaturated group (II-III) in this order”, “In order closer to the polysiloxane chain, a hydrocarbon group having 1 to 20 carbon atoms that may have an ether bond (II- I), a structure (II-II) containing a bond A or a bond B, and a structure containing a polymerizable unsaturated group (II-III) in this order”.

When at least one of the components (a-2) and (a-3), and the optionally used component (a-1-2) has a branched structure, the general formula of compound (a) ( 1) may include the structure of general formula (3) and/or general formula (4). The structure of general formula (1) of compound (a) of the present disclosure may be linear, partially linear, branched, or partially branched. . It is believed that the smaller the number of branches, the easier the peeling tends to be when the composition containing the compound (a) of the present disclosure is used as a release layer, and the larger the number of branches, the better the suppression of silicone transfer. I think there is a trend.

（一般式（３）中、
（ＩＶ）は、結合Ａ又は結合Ｂであり、
（Ｖ）は、炭素数１以上５０以下の直鎖状若しくは分岐状炭化水素基であり、
ｐは、１以上２０以下の整数であり、
線は、一般式（１）の（Ｉ－Ｉ）若しくは（ＩＩ－Ｉ）への結合、一般式（１）の（Ｉ－ＩＩ）若しくは（ＩＩ－ＩＩ）のさらなる単位への結合、又は一般式（１）の（Ｉ－ＩＩＩ）若しくは（ＩＩ－ＩＩＩ）への結合である。） General formula (3):

(In general formula (3),
(IV) is bond A or bond B;
(V) is a linear or branched hydrocarbon group having 1 to 50 carbon atoms,
p is an integer of 1 or more and 20 or less,
The line is a bond to (II) or (II-I) of general formula (1), a bond to a further unit of (I-II) or (II-II) of general formula (1), or the general A bond to (I-III) or (II-III) of formula (1). )

The “linear or branched hydrocarbon group having 1 to 50 carbon atoms” in (V) of general formula (3) means a linear hydrocarbon group having 1 to 50 carbon atoms or Refers to the following branched hydrocarbon groups. The upper limit of the carbon number of (V) in the general formula (3) is 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc. are exemplified, and the lower limits are exemplified by 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, and the like. In one embodiment, the number of carbon atoms in (V) in general formula (3) is preferably about 1 or more and 50 or less. The linear or branched hydrocarbon group having 1 to 50 carbon atoms in (V) of the general formula (3) is represented by C _δ H _2δ-1 (δ is an integer of 1 to 50). Structures are exemplified.

（一般式（４）中、
（ｉｖ）は、結合Ａ又は結合Ｂであり、
（ｖ）及び（ｖ）’は、それぞれ独立に、炭素数１以上２５以下の直鎖状若しくは分岐状炭化水素基であり、
ｐは、１以上２０以下の整数であり、
線は、一般式（１）の（Ｉ－Ｉ）若しくは（ＩＩ－Ｉ）への結合、一般式（１）の（Ｉ－ＩＩ）若しくは（ＩＩ－ＩＩ）のさらなる単位への結合、又は一般式（１）の（Ｉ－ＩＩＩ）若しくは（ＩＩ－ＩＩＩ）への結合である。） General formula (4):

(In the general formula (4),
(iv) is bond A or bond B;
(v) and (v)' are each independently a linear or branched hydrocarbon group having 1 to 25 carbon atoms,
p is an integer of 1 or more and 20 or less,
The line is a bond to (II) or (II-I) of general formula (1), a bond to a further unit of (I-II) or (II-II) of general formula (1), or the general A bond to (I-III) or (II-III) of formula (1). )

The “linear or branched hydrocarbon group having 1 to 25 carbon atoms” in (v) and (v)′ of general formula (4) means a linear hydrocarbon group having 1 to 25 carbon atoms or It refers to a branched hydrocarbon group having 1 or more and 25 or less carbon atoms. The upper limits of the number of carbon atoms of (v) and (v)' in the general formula (4) are each independently exemplified by 25, 20, 15, 10, 5, 4, 3, 2, etc., and the lower limits are 20, 15, 10, 5, 4, 3, 2, 1, etc. are exemplified. In one embodiment, the number of carbon atoms of (v) and (v)' in general formula (4) is preferably about 1 or more and 25 or less. C _ε H _2ε (ε is an integer of 1 or more and 25 or less) as a linear or branched hydrocarbon group having 1 or more and 25 or less carbon atoms in (v) and (v)′ of general formula (4). ) are exemplified.

p in general formula (3) and general formula (4) indicates the number of occurrences of general formula (3) or general formula (4) in general formula (1). The upper limits of p in general formulas (3) and (4) are exemplified by 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc., and the lower limits are 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc. are exemplified. In one embodiment, p in general formulas (3) and (4) is preferably about 1 or more and 20 or less.

Compound (a) is a reactant of components including components (a-1), (a-2) and (a-3). The method for synthesizing compound (a) is not particularly limited, but it is conceivable to carry out the reactions in the order described below. In the reaction, it is also conceivable to obtain compound (a) that does not partially proceed with the reaction by adopting a method such as adjusting the number of moles of (the functional groups possessed by) each component.
(1) Method of reacting component (a-1) with component (a-2) and then reacting component (a-3) (2) component (a-1) and component (a-2) After reacting with the component, the (a-3) component is reacted, then the (a-2) component is reacted, and the (a-3) component is further reacted (3) with the (a-1) component , after reacting the component (a-2), the component (a-3) is reacted, then the component (a-2) is reacted, the component (a-3) is reacted, and then the component (a -2) Method of reacting components and finally reacting component (a-3)

Among the above methods for synthesizing compound (a), in (1) bond A-bond B are formed in this order, in (2) bond A-bond B-bond A-bond B are formed in this order, ( In 3), bond A-bond B-bond A-bond B-bond A-bond B are formed in this order. When component (a-1) contains bond B, bond B-bond A-bond B is formed in this order in (1), and bond B-bond A-bond B-bond A in (2). -bond B is formed in this order, and in (3) bond B-bond A-bond B-bond A-bond B-bond A-bond B is formed in this order. That is, general formula (5) is exemplified as the arrangement order of bond A and bond B in a structure containing bond A and bond B possessed by compound (a) of the present disclosure.

General formula (5): [(bond B)] _κ [(bond A) (bond B)] _ζ
(In general formula (5),
K is 0 or 1;
ζ is an integer of 1 or more and 3 or less. )

The upper limit of ζ in general formula (5) is exemplified as 3, 2, etc., and the lower limit is exemplified as 2, 1, etc. In one embodiment, ζ in general formula (5) is preferably about 1 or more and 3 or less.

Among the bonds possessed by compound (a), bond A (that is, one or more bonds selected from structural formulas (1) to (3)) is, for example, the thiol group or amino group in component (a-2). It is obtained by progressing a reaction with the polymerizable unsaturated group in component (a-1) or component (a-3). The reaction can also be carried out in the presence of a catalyst, for example, at a specific temperature. The specific temperature is preferably about 50-120°C, more preferably 60-100°C. Bond B (that is, urethane bond) is obtained, for example, by reaction between the hydroxyl group of component (a-2) and the isocyanate group of component (a-3). The reaction can also be carried out in the presence of a catalyst, for example, at a specific temperature. The specific temperature is preferably about 50-120°C, more preferably 60-100°C. As a solvent for these reactions, one or more selected from ketone solvents, aromatic solvents and ester solvents are preferably used.

The upper limit of the number average molecular weight of component (a) is 500, 18,000, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000, 14,500, 14,000, 13,500, 13,000, 12,500, 12,000, 11,500, 11,000, 10,500, 10,000, 9,500, 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,500, 000, 5,500, 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, etc., and the lower limits are 45,000, 40, 000, 35,000, 30,000, 25,000, 20,000, 19,500, 19,000, 18,500, 18,000, 17,500, 17,000, 16,500, 16,000, 15,500, 15,000, 14,500, 14,000, 13,500, 13,000, 12,500, 12,000, 11,500, 11,000, 10,500, 10,000, 9, 500, 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, 1,000 and the like are exemplified. In one embodiment, the number average molecular weight of component (a) is preferably about 1,000 to 50,000.

Compounds (a) of the present disclosure are exemplified by chemical formulas 16 to 19 and the like. Chemical formula 16 has octafunctionality at one end on the right side, Chemical formula 17 has octafunctionality on one end on the right side and difunctionality on one end on the left side, Chemical formula 18 has octafunctionality on one end on the right side, and one end on the left side It has pentafunctionality at the terminal, and Chemical formula 19 has octafunctionality at both ends.

<Component that can be used in combination with compound (a)>
Compound (a) of the present disclosure contains 4 or more polymerizable unsaturated groups and is therefore contemplated for use in situations known in the art to employ polymerizable unsaturated groups. For example, for the compound (a) of the present disclosure, components applied when performing various polymerizations (a component containing two or more (meth)acryloyl groups, a component containing a thiol group (SH group), an initiator, organic solvent, etc.). Of the components that can be used in combination with the compound (a) of the present disclosure, the component (b) containing two or more (meth)acryloyl groups, the photopolymerization initiator (c), the organic solvent (d), etc. are shown in detail. In the present disclosure, a composition containing components (a), (b), and (c) is also referred to as an active energy ray-curable coating composition. Moreover, it is particularly preferable to use the active energy ray-curable coating composition of the present disclosure as a release coating composition because it is excellent in light releasability and the like.

The upper limit of the content (in terms of solid content) of component (a) in the total 100% by mass (in terms of solid content) of components (a), (b) and (c) is 50, 40, 30, 20, 10, 8, 6, 4, 2, 1.8, 1.6, 1.4, 1.2, 1.0, 0.8, 0.6, 0.4, 0.2, 0.1 mass % etc. are exemplified, and the lower limits are 40, 30, 20, 10, 8, 6, 4, 2, 1.8, 1.6, 1.4, 1.2, 1.0, 0.8, 0 .6, 0.4, 0.2, 0.1, 0.05% by mass and the like are exemplified. In one embodiment, the range of the content (in terms of solid content) of component (a) in the total 100% by mass (in terms of solid content) of components (a), (b) and (c) is 0.05. About 10% by mass is preferable.

<Component (b) containing two or more (meth)acryloyl groups>
As the component (b) containing two or more (meth)acryloyl groups (also referred to as "component (b)" in the present disclosure), a compound having a chain structure and two or more (meth)acryloyl groups , a compound containing an alicyclic hydrocarbon group and having two or more (meth)acryloyl groups, a compound containing an aromatic hydrocarbon group and having two or more (meth)acryloyl groups, and the like. In the present disclosure, a chain structure refers to a structure that does not have a cyclic structure, and may include a straight chain or a branched structure.

The component (b) may be a compound further having one or more functional groups other than a (meth)acryloyl group or a specific bond. Examples of functional groups and specific bonds other than (meth)acryloyl groups include urethane bonds, ether bonds, ester bonds, amide bonds, thioether bonds, hydroxyl groups, carboxyl groups, and amino groups. The component (b) may also be an EO-modified, PO-modified or caprolactone-modified compound having two or more (meth)acryloyl groups. A compound having a urethane bond and two or more (meth)acryloyl groups is a reaction product of a compound having a hydroxyl group and two or more (meth)acryloyl groups and various known polyfunctional isocyanates. may In the present disclosure, polyfunctional isocyanate refers to those having two or more isocyanate groups (-N=C=O).

Compounds having a chain structure and two or more (meth)acryloyl groups include a chain structure di(meth)acrylate, a chain structure tri(meth)acrylate, a chain structure tetra(meth) ) acrylate, chain structure penta(meth)acrylate, chain structure hexa(meth)acrylate, and the like.

Examples of di(meth)acrylates having a chain structure include 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth) ) acrylate, butanediol di(meth)acrylate, bis(methacryloyloxy)propanol, decanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, polytetraethylene glycol di(meth)acrylate Examples include acrylates, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate and the like.

Examples of tri(meth)acrylates having a chain structure include pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate.

Examples of tetra(meth)acrylates having a chain structure include pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate.

Dipentaerythritol penta(meth)acrylate etc. are illustrated as penta(meth)acrylate which is a chain structure.

Examples of hexa(meth)acrylate having a chain structure include dipentaerythritol hexa(meth)acrylate, hexafunctional aliphatic urethane(meth)acrylate (product name “Miramer PU-610”, manufactured by Miwon Specialty Chemical Co., Ltd.), and the like. be done.

Other (meth)acrylates having a chain structure include 16-20 functional acrylates having a dendrimer structure (product name “Sirius-501”, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Di(meth)acrylate etc. which have an alicyclic hydrocarbon group are illustrated as a compound which has an alicyclic hydrocarbon group and has two or more (meth)acryloyl groups.

Examples of di(meth)acrylates having an alicyclic hydrocarbon group include tricyclodecanedimethanol di(meth)acrylate and dimethyloltricyclodecanedi(meth)acrylate.

Di(meth)acrylate etc. which have an aromatic-hydrocarbon group are illustrated as a compound which has an aromatic-hydrocarbon group and has two or more (meth)acryloyl groups.

Di(meth)acrylates having an aromatic hydrocarbon group include bisphenol A di(meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, bis(meth)acrylic acid Examples include [3,3′-[isopropylidenebis(p-phenyleneoxy)]bis(2-hydroxypropane)]-1,1′-diyl, bisphenol A diglycidyl ether (meth)acrylic acid adducts, and the like. . (Meth)acrylic acid means methacrylic acid and/or acrylic acid.

Examples of heterocycle-containing (meth)acrylates include ethoxylated isocyanuric acid tri(meth)acrylate, caprolactone-modified tris((meth)acryloxyethyl)isocyanurate, and the like.

Other components containing two or more (meth)acryloyl groups include polyurethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, and the like.

Various known methods are exemplified as methods for synthesizing polyurethane (meth)acrylate. Various known methods for synthesizing polyurethane (meth)acrylate include: (1) a method of subjecting an isocyanate group-terminated prepolymer obtained by urethanizing a polyol and a polyisocyanate to a urethanization reaction with a hydroxyl group-containing (meth)acrylate;
(2) A method of reacting a hydroxyl group-terminated prepolymer obtained by a urethanization reaction of a polyol and a polyisocyanate with an isocyanate group-containing (meth)acrylate,
(3) A method of reacting a polyisocyanate and a hydroxyl group-containing (meth)acrylate is exemplified.
In these methods, it is conceivable to appropriately use various known catalysts (dibutyltin dilaurate, etc.) as necessary.

Polyols such as polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, polyolefin polyol, neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6 -hexanediol, trimethylolpropane, pentaerythritol, tricyclodecanedimethylol, bis-[hydroxymethyl]-cyclohexane and the like. Substances exemplified as polyols and known polyols can be used alone or in combination of two or more.

Examples of polyether polyols include polyalkylene glycols (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.). As polyether polyols, commercially available products may be used. Examples of such products include the product names "ADEKA Polyether P Series", "ADEKA Polyether G Series", and "ADEKA Polyether EDP Series" (manufactured by ADEKA Corporation).

Examples of polyester polyols include those obtained by reacting polyols with polycarboxylic acids (succinic acid, phthalic acid, malonic acid, maleic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, etc.), cyclic esters (propiolactone, β-methyl-δ-valerolactone, ε-caprolactone, etc.), and a three-way reaction product of polyol, polycarboxylic acid and cyclic ester. Commercially available products may be used as polyester polyols. Such products include the product names "Kuraray Polyol P Series", "Kuraray Polyol F Series" (manufactured by Kuraray Co., Ltd.), product name "PLAXEL 205" (manufactured by Daicel Corporation), and product name "Polylite OD-X-2155." ” (manufactured by DIC Corporation) and the like are exemplified.

Examples of polycarbonate polyols include reaction products of polyols and phosgene, ring-opening polymers of cyclic carbonates (such as alkylene carbonates), and the like. Examples of alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate and the like. A commercially available product may be used as the polycarbonate polyol. Examples of such products include the product name "Kuraray Polyol C Series" (manufactured by Kuraray Co., Ltd.).

Examples of acrylic polyols include homopolymers or copolymers of acrylic monomers containing one or more hydroxyl groups in one molecule, or those obtained by copolymerizing these copolymers with other monomers. . A commercially available product may be used as the acrylic polyol. Examples of such products include the product name "ARUFON UH-2000 Series" (manufactured by Toagosei Co., Ltd.).

Examples of polyolefin polyols include polybutadiene containing two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorinated products thereof. A commercially available product may be used as the polyolefin polyol. Examples of such products include the product name "NISSO-PB GI Series" (manufactured by Nippon Soda Co., Ltd.).

Examples of polyisocyanates include isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, dicyclopentanyl isocyanate, and the like. are exemplified. Examples of other polyisocyanates include the above-exemplified polyisocyanates, adducts of various known polyisocyanates, polymers of these isocyanates, and the like. Examples of such polyisocyanates include biurets, nurates, adducts, allophanates and the like. Examples of polyisocyanate biuret include product names "Duranate 24A-100", "Biuret 22A-75P", and "Biuret 21S-75E" (all manufactured by Asahi Kasei Corporation). Examples of polyisocyanate nurate include product names "Coronate HK" and "Coronate HXR" (both manufactured by Tosoh Corporation). Examples of polyisocyanate adducts include the product name "Coronate HL" (manufactured by Tosoh Corporation). Examples of allophanates of polyisocyanates include the product name "Coronate 2770" (manufactured by Tosoh Corporation). The polyisocyanate of the present disclosure also has an average number of isocyanate groups of about 3 to 10. In addition, the average number of isocyanate groups can be calculated by the following formula. Average number of isocyanate groups = (number average molecular weight (Mn) x isocyanate group concentration (%))/(42.02 x 100). The isocyanate group concentration (%) in the formula is a value measured by the method described in JIS K 1603-1:2007. The substances exemplified as polyisocyanates and those known as polyisocyanates can be used alone or in combination of two or more.

Examples of hydroxyl group-containing (meth)acrylates include 1-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) ) acrylate, hydroxycyclohexyl (meth)acrylate, 4-(hydroxymethyl)cyclohexylmethyl (meth)acrylate, hydroxyphenyl (meth)acrylate, pentaerythritol tri (meth)acrylate, dipentaerythritol tetra (meth)acrylate, dipentaerythritol penta(meth)acrylate and the like. Substances exemplified as hydroxyl group-containing (meth)acrylates and known hydroxyl group-containing (meth)acrylates can be used alone or in combination of two or more.

Examples of isocyanate group-containing (meth)acrylates include 2-(meth)acryloyloxyethyl isocyanate and 1,1-(bisacryloyloxymethyl)ethyl isocyanate. Substances exemplified as isocyanate group-containing (meth)acrylates and known isocyanate group-containing (meth)acrylates can be used alone or in combination of two or more.

Various known methods are exemplified as methods for synthesizing the polyester (meth)acrylate. Various known methods for synthesizing polyester (meth)acrylates include: (1) a hydroxyl group-terminated polyester obtained by reacting a polycarboxylic acid and a polyol, and a carboxyl group-containing (meth)acrylate (carboxyethyl (meth)acrylate, carboxypolycaprolactone mono (meth) acrylate, etc.),
(2) A method of reacting a hydroxyl group-containing (meth)acrylate with a carboxyl group-terminated polyester obtained by reacting a polycarboxylic acid and a polyol is exemplified.
In these methods, it is conceivable to appropriately use various known catalysts as necessary.

As an epoxy (meth)acrylate, a carboxyl group-containing (meth)acrylate is added to an epoxy resin containing at least two epoxy groups in one molecule (bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, etc.). Those obtained by reacting are exemplified.
In these methods, it is conceivable to appropriately use various known catalysts as necessary.

A commercially available product may be used as the component containing two or more (meth)acryloyl groups. Examples of such products include pentaerythritol triacrylate ((product names “A-TMM-3”, “A-TMM-3L”, manufactured by Shin-Nakamura Chemical Co., Ltd.), (product name “Miramer M301”, manufactured by MIWON). , (product name “Aronix M-309”, manufactured by Toagosei Co., Ltd.), ditrimethylolpropane tetraacrylate (product name “Aronix M-408”, manufactured by Toagosei Co., Ltd.), ethoxylated pentaerythritol tetra (meth ) acrylate (product name “SR494”, manufactured by Sartomer), dipentaerythritol penta (meth) acrylate (product name “SR399”, manufactured by Sartomer), dipentaerythritol poly (meth) acrylate (dipentaerythritol penta (meth) mixture of acrylate and dipentaerythritol hexa(meth)acrylate) ((product name “KAYARAD DPHA”, manufactured by Nippon Kayaku Co., Ltd.), (product name “A-9550”, manufactured by Shin-Nakamura Chemical Co., Ltd.), (Product name "Aronix M-403", "Aronix M-400", "Aronix M-402", "Aronix M-404", "Aronix M-405", "Aronix M-406", Toagosei Co., Ltd. )), tripentaerythritol poly(meth)acrylate (product name “Viscoat #802, TriPEA”, manufactured by Osaka Organic Chemical Industry Co., Ltd.), polyfunctional acrylate containing a dendrimer structure (product name “Sirius-501”, “ SUBARU-501", manufactured by Osaka Organic Chemical Industry Co., Ltd.), urethane (meth)acrylate (product names "UV1700B", "UV7620EA", "UV7610B", "UV7600B", "UV7650B", manufactured by Mitsubishi Chemical Corporation) , (product name “DPHA40H”, “UX5003”, manufactured by Nippon Kayaku Co., Ltd.), (product name “Beamset 577”, manufactured by Arakawa Chemical Industries, Ltd.), (product name “8UX-015A”, Taisei Fine Chemical Co., Ltd.), (product name “U15HA”, manufactured by Shin-Nakamura Chemical Co., Ltd.), (product name “Miramer PU610”, manufactured by Miwon Specialty Chemical) (product name “Etercure 6196-100”, Eternal Materials) (manufactured by Toagosei Co., Ltd.), bisphenol A type epoxy acrylate (product name “Aronix OT-2501”, manufactured by Toagosei Co., Ltd.), and the like.

Substances exemplified as components containing two or more (meth)acryloyl groups and known components containing two or more (meth)acryloyl groups can be used alone or in combination of two or more. .

A component containing two or more (meth)acryloyl groups is particularly easy to cure even when the dose of active energy rays is reduced, and the composition of the present disclosure has good peelability when used as a peeling layer. It is preferably a compound containing a hydroxyl group and two or more (meth)acryloyl groups, more preferably a compound containing a hydroxyl group, a chain hydrocarbon group and two or more (meth)acryloyl groups, still more preferably. is pentaerythritol poly(meth)acrylate and/or dipentaerythritol poly(meth)acrylate, particularly preferably a mixture of pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate and/or dipentaerythritol penta( It is a mixture of meth)acrylate and dipentaerythritol hexa(meth)acrylate.

The upper limit of the carbon number of the component containing two or more (meth)acryloyl groups is exemplified by 200, 150, 100, 80, 60, 50, 40, 30, 20, 10, etc., and the lower limit is 100, 80, 60, 50, 40, 30, 20, 10, 8, 6, 4, etc. are exemplified. In one embodiment, the number of carbon atoms in the component containing two or more (meth)acryloyl groups is preferably about 4 to 200.

The upper limit of the number of (meth)acryloyl groups contained in the component containing two or more (meth)acryloyl groups is 30, 25, 20, 18, 16, 15, 10, 8, 6, 5, 4, 3, etc. are exemplified, and the lower limit is exemplified by 16, 15, 10, 8, 6, 5, 4, 3, 2, and the like. In one embodiment, the number of (meth)acryloyl groups contained in the component containing two or more (meth)acryloyl groups is preferably about 2 to 30.

The upper limit of the molecular weight of the component containing two or more (meth)acryloyl groups is 50,000, 40,000, 30,000, 20,000, 10,000, 5,000, 1,000, 500, 250, etc. are exemplified, and the lower limits are exemplified by 40,000, 30,000, 20,000, 10,000, 5,000, 1,000, 500, 250, 100, 50, and the like. In one embodiment, the molecular weight of component (b) is preferably about 50 to 5,000.

The upper limits of the mass ratio of the solid content of components (a) and (b) (component (a)/component (b)) are 50/50, 40/60, 30/70, 20/80, 10/90, 8/92, 6/94, 4/96, 2/98, 1/99, 0.8/99.2, 0.6/99.4, 0.4/99.6, 0.2/99. 8, etc., and the lower limits are 40/60, 30/70, 20/80, 10/90, 8/92, 6/94, 4/96, 2/98, 1/99, 0.8/99 .2, 0.6/99.4, 0.4/99.6, 0.2/99.8, 0.1/99.9 and the like. In one embodiment, the mass ratio of the solid content of components (a) and (b) (component (a)/component (b)) is preferably about 0.1/99.9 to 50/50.

The upper limit of the content (in terms of solid content) of component (b) in the total 100% by mass (in terms of solid content) of components (a), (b) and (c) is 98, 96, 94, 92, Examples include 90, 85, 80, 75, 70, 65, 60, 55% by mass, etc., and the lower limit is 96, 94, 92, 90, 85, 80, 75, 70, 65, 60, 55, 50% by mass. etc. are exemplified. In one embodiment, the content (in terms of solid content) of component (b) in the total 100% by mass (in terms of solid content) of components (a), (b) and (c) is in the range of 50 to 98. About % by mass is preferable.

<Photoinitiator (c)>
A photopolymerization initiator (c) (also referred to as “(c) component” in the present disclosure) is exemplified as a component that can be used in combination with the compound (a) of the present disclosure. Examples of photopolymerization initiators include radical photopolymerization initiators, cationic photopolymerization initiators, anionic photopolymerization initiators, and the like.

Examples of radical photopolymerization initiators include alkylphenone type photopolymerization initiators, acylphosphine oxide type photopolymerization initiators, hydrogen abstraction type photopolymerization initiators, oxime ester type photopolymerization initiators, and the like.

As alkylphenone-type photopolymerization initiators, benzyl dimethyl ketal such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy- 2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one , α-hydroxyalkylphenones such as 1-hydroxycyclohexylphenyl ketone, α-aminoalkylphenones such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and the like. be.

Examples of acylphosphine oxide type photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

Examples of the hydrogen abstraction type photopolymerization initiator include phenylglyoxylic acid methyl ester and the like.

As oxime ester type photopolymerization initiators, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2- Methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and the like are exemplified.

a mixture of iodonium, (4-methylphenyl)]4-(2-methylpropyl)phenyl]-hexafluorophosphate (1-) and propylene carbonate, triarylsulfonium hexafluorophosphate, as cationic photoinitiators; Triarylsulfonium tetrakis-(pentafluorophenyl)borate and the like are exemplified.

Examples of anionic photopolymerization initiators include cobalt amine complexes, o-nitrobenzyl alcohol carbamate esters, oxime esters, and the like.

Since the photopolymerization initiator has excellent curing speed, it is preferably a radical photopolymerization initiator, more preferably an alkylphenone type photopolymerization initiator, still more preferably α-aminoalkylphenone and/or α-hydroxy alkylphenone, particularly preferably 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2- methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one and one or more selected from 1-hydroxycyclohexylphenyl ketone.

A commercially available product may be used as a photoinitiator. Examples of such products include 2,2-dimethoxy-1,2-diphenylethan-1-one (product name “Omnirad (hereinafter also referred to as “Omnirad”) 651” manufactured by IGM Resins), 1-[4-( 2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (product name “Omnilad 2959”, manufactured by IGM Resins), 2-hydroxy-1-{4-[4- (2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (product name “Omnilad 127”, manufactured by IGM Resins), 2-methyl-1-(4-methylthio Phenyl)-2-morpholinopropan-1-one (product name “Omnilad 907”, manufactured by IGM Resins), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (product name “Omnilad TPO H”, IGM Resins), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (product name “Omnilad 819”, IGM Resins), phenylglyoxylic acid methyl ester (product name “Omnilad MBF”, IGM Resins), 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (product name “IRGACURE OXE 01”, manufactured by BASF Japan Ltd.), ethanone , 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (product name “IRGACURE OXE 02”, manufactured by BASF Japan Co., Ltd. ), iodonium, (4-methylphenyl)]4-(2-methylpropyl)phenyl]-hexafluorophosphate (1-) and a mixture of propylene carbonate (product name “Omnicat” (hereinafter also referred to as “Omnicat”). ) 250”, manufactured by IGM Resins), triarylsulfonium hexafluorophosphate (product name “Omnicat 270”, manufactured by IGM Resins), triarylsulfonium tetrakis-(pentafluorophenyl)borate (product name “IRGACURE 290 ”, manufactured by BASF Japan Ltd., etc. are exemplified.

The substances exemplified as photopolymerization initiators and known photopolymerization initiators can be used alone or in combination of two or more.

The upper limits of the mass ratio of the solid content of components (a) and (c) (component (a)/component (c)) are 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/80, 15/85, 10/90, 5/95, etc. are exemplified, and the lower limits are 65/35, 60/40 , 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/80, 15/85, 10/90, 5/95, 1/99, etc. exemplified. In one embodiment, the mass ratio of the solid content of components (a) and (c) (component (a)/component (c)) is preferably about 1/99 to 70/30.

The upper limits of the mass ratio of the solid content of components (b) and (c) (component (b)/component (c)) are 99/1, 95/5, 90/10, 85/15, 80/20, Examples include 75/25, and lower limits include 95/5, 90/10, 85/15, 80/20, 75/25, and 70/30. In one embodiment, the mass ratio of the solid content of components (b) and (c) (component (b)/component (c)) is preferably about 70/30 to 99/1.

The upper limits of the content (in terms of solid content) of component (c) in the total 100% by mass (in terms of solid content) of components (a), (b) and (c) are 30, 25, 20, 18, 16, 14, 12, 10, 8, 6, 4, 2% by mass, etc. are exemplified, and the lower limit is 25, 20, 18, 16, 14, 12, 10, 8, 6, 4, 2, 1% by mass. etc. are exemplified. In one embodiment, the content (in terms of solid content) of component (c) in the total 100% by mass (in terms of solid content) of components (a), (b) and (c) is in the range of 1 to 30. About % by mass is preferable.

<Other agents that can be added>
The compound (a) of the present disclosure may optionally further contain binder resins other than the components exemplified above (acrylic resins, urethane resins, polyester resins, epoxy resins, alkyd resins, etc.), anti-slip agents, slip agents, preservatives. , antirust agents, pH adjusters, pigments, dyes, lubricants, leveling agents, catalysts, antifoaming agents, photosensitizers (amines, quinones, etc.) and other additives may also be added. It is also conceivable to incorporate an antioxidant such as a hindered amine, an amine-containing compound such as triethanolamine, or a component containing a thiol group (SH group). A component containing a thiol group (SH group) is contemplated to be incorporated into a composition comprising compound (a) of the present disclosure in order to cure the composition comprising compound (a) of the present disclosure via a thiol/ene reaction. be done. As the component containing a thiol group (SH group), various known ones can be used alone or in combination of two or more. For example, a component containing a thiol group (SH group) described in JP-A-2013-231167 and a component containing a thiol group (SH group) described in JP-A-2013-213200 are exemplified.

If necessary, the composition containing the compound (a) of the present disclosure is blended with an organic solvent (d) (also referred to as "(d) component" in the present disclosure), and the viscosity is adjusted before use. is also possible. Various known organic solvents may be used. Examples of organic solvents include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, haloalkane solvents, amide solvents and the like.

Examples of ketone solvents include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and the like.

Examples of aromatic solvents include toluene and xylene.

Examples of alcohol solvents include methanol, ethanol, n-propanol, isopropanol, butanol and the like.

Examples of glycol solvents include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol and the like.

Glycol ether solvents include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, Examples include ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-t-butyl ether and the like.

Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate and the like.

Examples of petroleum solvents include Solvesso #100 (manufactured by Exxon), Solvesso #150 (manufactured by Exxon) and the like.

Chloroform etc. are illustrated as a haloalkane solvent.

Examples of amide solvents include dimethylformamide and the like.

The substances exemplified as organic solvents and known organic solvents can be used alone or in combination of two or more.

<Laminate>
A cured product obtained by irradiating a composition containing the compounds (a), (b) and (c) with an active energy ray is also disclosed. Also provided by the present disclosure is a laminate comprising a substrate and a cured composition of the present disclosure. The present disclosure also provides a method of manufacturing a laminate, which comprises the step of curing the composition of the present disclosure coated on at least one side of a substrate with active energy rays.

Examples of substrates to which the composition of the present disclosure is applied include glass substrates, metal substrates, plastic substrates, and the like. Examples of plastic substrates include thermoplastic plastic substrates, thermosetting plastic substrates, and the like. Examples of thermoplastic plastic substrates include general-purpose plastic substrates, engineering plastic substrates, and the like. Examples of general-purpose plastic substrates include olefin-based, polyester-based, acrylic-based, vinyl-based, polystyrene-based, and the like. Examples of olefin-based materials include polyethylene, polypropylene, norbornene, and the like. Examples of polyester-based materials include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Examples of acrylic materials include polymethyl methacrylate (PMMA). Examples of vinyl-based materials include polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol. Examples of polystyrene-based resins include polystyrene (PS) resin, styrene-acrylonitrile (AS) resin, styrene-butadiene-acrylonitrile (ABS) resin, and the like. Examples of engineering plastic substrates include general-purpose engineering plastics, super engineering plastics, and the like. Examples of general-purpose engineering plastics include polycarbonate and polyamide (nylon). Examples of super engineering plastics include polyetheretherketone (PEEK). Examples of thermosetting plastic substrates include polyimide, epoxy resin, and melamine resin. Examples of other plastic substrates include triacetyl cellulose resin and the like. Further, the base material may be subjected to surface treatment (such as corona discharge). In addition, on one or both sides of the substrate, other layers (for example, an easy-adhesion layer, an anchor layer, etc.) may be provided between the layers formed by the composition of the present disclosure. The substrate is preferably a polyester-based film, more preferably a polyethylene terephthalate film, because it is excellent in transparency, dimensional stability, mechanical properties, chemical resistance, and the like. The thickness of the base material is not particularly limited, and is usually about 1 to 150 μm.

Methods for coating the composition of the present disclosure on a substrate include roll coater coating, reverse roll coater coating, bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, Offset printing, flexographic printing, screen printing and the like are exemplified. Although the coating amount is not particularly limited, it is usually in the range where the mass after drying is 0.01 to 20 g/m ² , preferably 0.025 to 10 g/m ² , more preferably 0. .05 to 5 g/m ² . Further, the film thickness of the cured product of the composition of the present disclosure is about 0.05 to 10 μm.

As a method for curing the composition of the present disclosure by irradiation with active energy rays, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, and non-radiation lamps that emit light in the wavelength range of 150 nm or more and 450 nm or less. A method of irradiating about 10 mJ/cm ² or more and 10,000 mJ/cm ² or less using an electrode discharge lamp or an LED is exemplified. Before the active energy ray irradiation, it may be dried by heating if necessary. After the active energy ray irradiation, heating may be performed as necessary for complete curing. As the heating conditions, about 60 to 150° C. and about 30 seconds to 30 minutes are exemplified, and preferably 70 to 130° C. and about 50 seconds to 10 minutes are considered.

The laminate of the present disclosure may be subjected to curing treatment if necessary. Although the conditions are not particularly limited, they are about 20 to 50° C. for 1 to 24 hours. By carrying out like this, the solvent resistance of hardened|cured material becomes more favorable.

Cured products of the compositions of the present disclosure can exhibit light release and solvent resistance. Therefore, the cured product of the composition can be coated with a material containing a large amount of an organic solvent, such as a casting solution for a resin molding or an inorganic slurry. A cured product of the composition of the present disclosure can be used as an adhesive tape or an adhesive tape by applying an adhesive layer on the opposite side of the cured product. In addition, the cured product of the composition of the present disclosure is an adhesive tape, adhesive tape, double-sided tape, adhesive label, adhesive surface protective film (separator) such as a seal, as well as resin molded products, synthetic leather, decorative boards, It is also useful as a process film used in the production of carbon fiber prepreg, electrical and electronic parts, and the like. The cured product of the composition of the present disclosure is a cured product that can suppress silicone migration. Therefore, it is used as a process film or process tape (e.g., separator, carrier film (tape), transfer film, protective tape, etc.) for the production of electrical and electronic materials, where the occurrence of defects due to migration of silicone from the cured product is particularly undesirable. Especially useful. In the present disclosure, the term "electrical/electronic materials" refers to parts that constitute a group of products having electronic circuits, such as personal computers, mobile phones, liquid crystal displays, refrigerators, automobiles, and the like. That is, the cured product of the present disclosure is useful as a release film and peeling film. In addition, the cured product of the composition of the present disclosure can suppress silicone migration even after the heating step. Therefore, process films or process tapes (e.g., separators, carrier films (tape), transfer films, protective tapes) for manufacturing electrical and electronic materials that include heating processes such as solvent drying, heat curing, and heat press bonding in the manufacturing process etc.).

In addition, it is conceivable that the compound (a) of the present disclosure may be used for various applications in which the effects exhibited by the compound (a) can be exhibited.

Specific examples of the present disclosure will be described below with reference to Examples, but the present disclosure is not limited to these examples. All parts and percentages in the examples are based on mass unless otherwise specified.

In each example, the number average molecular weight (Mn) was measured by gel permeation chromatography (GPC) under the following conditions.
(GPC measurement conditions)
Model: Product name “HLC-8220GPC” (manufactured by Tosoh Corporation)
Column: Product names "TSKgel G1000H" and "TSKgel G2000H" (manufactured by Tosoh Corporation)
Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL/min Measurement temperature: 40°C
Detector: Differential refractive index detector (RI: Refractive Index Detector)
Standard: monodisperse polystyrene sample: 20 μL of solution obtained by preparing a 0.5 g/mL tetrahydrofuran solution in terms of solid content and filtering the solution through a microfilter

<Production Example 1: Synthesis of compound (A-1)>
A reaction vessel equipped with a stirrer, a thermometer, and a cooling tube was charged with one-end hydroxyl-modified silicone (product name “Silaplane FM-0421”, JNC Co., Ltd., number average molecular weight 5,000), hereinafter “FM-0421”. ”), 3.7 parts of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (product name “Karenzu BEI”, manufactured by Showa Denko Co., Ltd., hereinafter “BEI”), and 0.1 part of methoquinone. 08 parts of tin octoate and 0.03 parts of tin octylate were charged, the temperature in the system was raised to about 80° C., and the temperature was maintained for about 1 hour. After confirming disappearance of the isocyanate peak by IR, the temperature in the system was lowered to about 50°C.
Then, 100 parts of toluene, 0.04 parts of diazabicycloundecene (product name “DBU”, manufactured by San-Apro Co., Ltd., hereinafter “DBU”) and 1-thioglycerol (product name “Blenmer TGL”, NOF After charging 3.4 parts of TGL (manufactured by Co., Ltd.), the temperature in the system was raised to about 80° C., and the temperature was maintained for about 2 hours. Then, after confirming that the acryloyl group signal disappeared by ¹ H-NMR, the temperature in the system was lowered to about 40°C.
Next, 14.9 parts of BEI and 0.16 parts of tin octylate were added, and then the temperature in the system was raised to about 80° C. and maintained for about 6 hours. Then, after confirming disappearance of the isocyanate peak by IR, the reaction system was cooled to obtain a solution of compound (A-1) having a solid content of 50% by weight. The compound (A-1) had a number average molecular weight of 6,200 and a number of polymerizable unsaturated groups (number of functional groups) of 8.

<Production Examples 2 to 6, 8, 11 to 12 and Comparative Production Example 1: Compounds (A-2) to (A-6), (A-8), (A-11) to (A-12) and ( Synthesis of A-C1)>
Production Examples 2 to 6, 8, 11 to 12 and Comparative Production Example 1 were carried out in the same manner as in Production Example 1, except that the compositions were changed to those shown in Tables 1 to 3, and compounds (A-2) to Solutions of (A-6), (A-8), (A-11) to (A-12) and a solution of (A-C1) were obtained.

<Production Example 7: Synthesis of compound (A-7)>
Production Example 7 was carried out in the same manner as in Production Example 1 except that the composition was changed to that shown in Table 2 and the toluene used in Production Example 1 was changed to cyclohexanone to obtain a solution of compound (A-7). .

<Production Example 9: Synthesis of compound (A-9)>
80.4 parts of acryloyl-modified silicone at both ends (product name "X-22-2445", JNC Co., Ltd., number average molecular weight 3,200) was placed in a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube. After charging 100 parts of toluene, 0.08 parts of methoquinone, 0.04 parts of DBU and 5.4 parts of TGL, the temperature in the system was raised to about 80° C. and kept for about 2 hours. Then, after confirming that the acryloyl group signal disappeared by ¹ H-NMR, the temperature in the system was lowered to about 40°C.
Next, after charging 14.2 parts of BEI and 0.16 parts of tin octylate, the temperature in the system was raised to about 80° C. and maintained for about 6 hours. Then, after confirming disappearance of the isocyanate peak by IR, the reaction system was cooled to obtain a solution of compound (A-9) having a solid content of 50% by weight.

<Production Example 10: Synthesis of compound (A-10)>
Into a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 74.5 parts of one-end dihydroxy-modified silicone (product name "Silaplane FM-DA26", manufactured by JNC Co., Ltd., hereinafter "DA26"), BEI 2.7 parts of , 0.08 parts of methoquinone and 0.03 parts of tin octylate were charged, then the temperature in the system was raised to about 80°C and kept at that temperature for about 1 hour. After confirming disappearance of the isocyanate peak by IR, the temperature in the system was lowered to about 50°C.
Next, 100 parts of toluene and 3.6 parts of diethanolamine (product name “diethanolamine (DEA)”, manufactured by Mitsui Chemicals, Inc., hereinafter “DEA”) were added, and the temperature in the system was raised to about 40°C. Warm and keep warm for about 2 hours. Then, after confirming that 80% of the acryloyl groups were consumed by amine value measurement, 19.1 parts of BEI and 0.16 parts of tin octylate were added, and the temperature in the system reached about 80°C. The temperature was raised and kept for about 6 hours. Then, after confirming disappearance of the isocyanate peak by IR, the reaction system was cooled to obtain a solution of compound (A-10) having a solid content of 50% by weight.

<Comparative Production Examples 2-3: Synthesis of compounds (A-C2) and (A-C3)>
In Comparative Production Example 2, 96.3 parts of DA26, 3.7 parts of BEI, 0.08 parts of methoquinone and 0.03 parts of tin octylate were added to a reaction vessel equipped with a stirrer, thermometer and cooling tube. After charging, the temperature inside the system was raised to about 80° C., and the temperature was maintained for about 1 hour. After confirming disappearance of the isocyanate peak by IR, the reaction system was cooled to obtain a compound (A-C2). In Comparative Production Example 3, compound (A-C3) was obtained in the same manner, except that the composition was changed to that shown in Table 2.

The meanings of terms in Tables 1 to 3 are as follows.
FM-0421: One-end hydroxyl-modified silicone (product name “Silaplane FM-0421” manufactured by JNC Corporation, number average molecular weight 5,000)
FM-3325: Amino-modified silicone at both ends (product name “Silaplane FM-3325” manufactured by JNC Corporation, number average molecular weight 10,000)
FM-DA26: One end dihydroxy-modified silicone (product name “Silaplane FM-DA26”, manufactured by JNC Corporation, number average molecular weight 15,0000)
FM-4425: hydroxy-modified silicone at both ends (product name “Silaplane FM-4425” manufactured by JNC Corporation, number average molecular weight 10,000)
X-22-2445: Acrylic-modified silicone at both ends (product name "X-22-2445", manufactured by Shin-Etsu Chemical Co., Ltd.)
AOI: 2-acryloyloxyethyl isocyanate (product name “Karenzu AOI”, manufactured by Showa Denko K.K.)
BEI: 1,1-(bisacryloyloxymethyl)ethyl isocyanate (product name “Karenzu BEI”, manufactured by Showa Denko K.K.)
TGL: 1-thioglycerol (product name “Blenmar TGL”, manufactured by NOF Corporation)
2MET: (product name “2-mercaptoethanol”, manufactured by Toyobo Co., Ltd.)
DEA: diethanolamine (product name “diethanolamine (DEA)”, manufactured by Mitsui Chemicals, Inc.)

The terminal functional group number was confirmed by ¹ H-NMR using the following method.
One end dihydroxy-modified silicone (product name “Silaplane FM-DA26”, manufactured by JNC Corporation, hereinafter “DA26”) and 1,1-(bisacryloyloxymethyl)ethyl isocyanate (product name “Karenzu BEI”, Showa Denko (manufactured by Co., Ltd., hereinafter referred to as "BEI") were mixed at the molar ratio shown in Table 4.
Next, the resulting mixture was measured by ¹ H-NMR, and the integral value of the signal (5.8 ppm) derived from the acryloyl group when the integral value of the signal (0 ppm) derived from the methyl group of polydimethylsiloxane was taken as 100. Obtained. Since BEI has two acryloyl groups at its terminal, a straight line representing a proportional relationship was obtained by plotting the number of acryloyl groups and the signal integral value derived from acryloyl groups.
When (A-3) obtained in Production Example 3 was measured by ¹ H-NMR, the signal (5.8 ppm) derived from the acryloyl group was integrated when the signal (0 ppm) derived from the methyl group of polydimethylsiloxane was taken as 100. Since the value was 1.52, it was confirmed that the number of terminal functional groups was 16 from the previously obtained straight line.
(A-1) to (A-2), (A-4) to (A-6) and (A-C1) to (A-C3) are obtained by the same method except that the silicone used is changed. The number of terminal functional groups was confirmed.

<Example 1: Preparation of composition (1)>
225 parts of dipentaerythritol polyacrylate (product name "Aronix M403", manufactured by Toagosei Co., Ltd.), a solution of the compound (A-1) obtained in Production Example 1 (solid content: 50%) of 4.55 and 23 parts of 1-hydroxycyclohexyl phenyl ketone (product name “OMNIRAD 184”, manufactured by IGM Resins) as a photopolymerization initiator, diluted with methyl ethyl ketone so that the solid content is 20%. ) was prepared.

<Examples 2 to 6 and Comparative Example 1: Preparation of compositions (2) to (6) and (C1)>
In Examples 2 to 6 and Comparative Example 1, except that the solution of compound (A-1) was changed to a solution of compounds (A-2) to (A-6) and a solution of (A-C1), respectively, Compositions (2) to (6) and (C1) were obtained in the same manner as in Example 1.

<Example 7: Preparation of composition (7)>
225 parts of dipentaerythritol polyacrylate (product name “NK Ester A-9550”, manufactured by Shin-Nakamura Chemical Co., Ltd.), a solution of the compound (A-1) obtained in Production Example 1 (solid content: 50% ) as 4.6 parts, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one as a photopolymerization initiator (product name “OMNIRAD907”, manufactured by IGM RESINS) 23 parts The ingredients were blended and diluted with methyl ethyl ketone to a solid content of 20% to prepare composition (7).

<Examples 8-9: Preparation of compositions (8)-(9)>
225 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (product name “Viscoat #300”, manufactured by Osaka Organic Chemical Industry Co., Ltd.), a solution of compound (A-3) obtained in Production Example 3 (solid minutes: 50%), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one as a photopolymerization initiator (product name “OMNIRAD907”, manufactured by IGM RESINS ) and diluted with methyl ethyl ketone to a solid content of 20% to prepare composition (8). In Example 9, composition (9) was prepared in the same manner, except that Viscoat #300 was changed to dipentaerythritol polyacrylate (product name "GM66G0A", manufactured by Kokusei Chemical Co., Ltd.). .

<Examples 10 to 21: Preparation of compositions (10) to (21)>
Examples 10 to 21 were carried out in the same manner as in Example 1, except that the formulations were changed as shown in the table below, and compositions (10) to (21) were prepared.

<Comparative Example 2: Preparation of composition (C2)>
225 parts of dipentaerythritol polyacrylate (product name "Aronix M403", manufactured by Toagosei Co., Ltd.), 2.27 parts of the solution of the compound (A-C2) obtained in Comparative Production Example 2, and photopolymerization initiation As an agent, 23 parts of 1-hydroxycyclohexylphenyl ketone (product name “OMNIRAD 184”, manufactured by IGM Resins) was blended and diluted with methyl ethyl ketone to a solid content of 20% to prepare composition (C2).

<Comparative Examples 3 to 4: Preparation of Compositions (C3) to (C4)>
Comparative Examples 3 and 4 were performed in the same manner as in Comparative Example 2, except that the solution of compound (A-C2) was changed to compound (A-C3) and DA26, respectively. (C4) was obtained.

<Evaluation Example 1: Production of Laminate (1)>
The composition (1) was applied to a polyethylene terephthalate film (thickness: 75 μm) with a bar coater #9 (film thickness: 2 μm after drying), dried at 80° C. for 1 minute, and then irradiated with active energy rays (ultraviolet irradiation, illuminance: 520 mW/cm ² , integrated light quantity: 200 mJ/cm ² ), and a laminate (1) was obtained.

<Evaluation Examples 2 to 21 and Comparative Evaluation Examples 1 to 4: Production of laminates (2) to (21) and (C1) to (C4)>
Evaluation Examples 2 to 21 and Comparative Evaluation Examples 1 to 4 were performed in the same manner as in Evaluation Example 1, except that the composition, film thickness, and integrated amount of light shown in the table were changed. 21) and (C1) to (C4) were obtained.

<Performance evaluation (1): peelability test>
After the laminate was left overnight, a polyester adhesive tape (product name "No. 31B", manufactured by Nitto Denko Corporation, 20 mm width) was adhered to the surface of the cured product while being crimped with a roller of 2 kg. and left for 30 minutes. Next, using a Tensilon universal testing machine (product name "RTC-1250A", manufactured by A&D Co., Ltd.), the adhesive tape is pulled horizontally at an angle of 180 ° C. (0.3 m / min) and peeled. The force (mN/20mm) required for this was measured.

<Performance evaluation (2): Solvent resistance test>
After the laminate was left overnight, the surface of the cured product was reciprocated 5 times with a cloth impregnated with MEK with a uniform force. Thereafter, a polyester adhesive tape (product name “No. 31B”, manufactured by Nitto Denko Corporation, 20 mm width) was adhered to the same portion while being crimped with a roller of 2 kg, and left at 23° C. for 30 minutes. Next, using a Tensilon universal testing machine (product name "RTC-1250A", manufactured by A&D Co., Ltd.), the adhesive tape is pulled horizontally at an angle of 180 ° C. (0.3 m / min) and peeled. The force (mN/20mm) required for this was measured. At that time, the degree of heavy release was evaluated according to the following criteria with respect to the value measured in performance evaluation (1).
AA: Less than 1.3 times A: 1.3 times or more and less than 2.0 times B: 2.0 times or more and less than 5.0 times C: 5.0 times or more

<Performance evaluation (3): Si migration evaluation test>
A polyester adhesive tape (product name “No. 31B”, manufactured by Nitto Denko Corporation, 20 mm width) was adhered to the cured surface of the laminate left overnight while being crimped with a roller of 2 kg, and the laminate was left at 23° C. for 30 minutes. I left it. Next, the polyester adhesive tape is peeled off, and the Si element content ratio of the surface in contact with the coated surface of the cured product is measured using a scanning X-ray photoelectron spectrometer (product name “PHI5000VersaProbeIII”, manufactured by ULVAC-Phi, Inc.). It was measured. The measured value (silicone transfer amount (wt%)) was evaluated according to the following criteria.
AA: Less than 5.0 wt% A: 5.0 wt% or more and less than 10.0 wt% B: 10.0 wt% or more and less than 15.0 wt% C: 15.0 wt% or more

The meanings of the terms in Tables 5-7 are as follows.
M403: A mixture of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate (product name “Aronix M-403”, manufactured by Toagosei Co., Ltd.))
9550W: Dipentaerythritol polyacrylate (product name “NK Ester A-9550W”, manufactured by Shin-Nakamura Chemical Co., Ltd.)
#300: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (product name “Viscoat #300”, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
66G0A: Dipentaerythritol polyacrylate (product name "GM66G0A", manufactured by Kokusei Chemical Co., Ltd.)
M305: pentaerythritol tri- and tetraacrylate (product name "Aronix M-305", manufactured by Toagosei Co., Ltd.)
184: 1-hydroxycyclohexyl phenyl ketone (product name “OMNIRAD 184”, manufactured by IGM Resins)
907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (product name “OMNIRAD907”, manufactured by IGM RESINS)
MEK: Methyl ethyl ketone IPA: Isopropanol when applied Nv (%): Active ingredient concentration when applied

Claims (6)

Component (a-1) containing a polymerizable unsaturated group and polysiloxane,
A component containing a thiol group and a hydroxyl group and / or a component containing an amino group and a hydroxyl group (a-2), and a component containing an isocyanate group and a polymerizable unsaturated group (a-3)
is a reactant of a component containing
(a-2) component has a molecular weight of 50 to 200,
The number of thiol groups or secondary amino groups in component (a-2) is one,
(a-3) component has a molecular weight of 100 to 300,
A compound (a) according to general formula (1), wherein the number of isocyanate groups in component (a-3) is one .
General formula (1):

(In general formula (1),
X ₁ to X ₂ and X ₅ to X ₆ are each independently an alkyl group having 1 to 4 carbon atoms,
X ₃ to X ₄ are each independently an alkyl group having 1 to 4 carbon atoms, and each repeating unit may be the same or different;
n is an integer of 1 or more and 400 or less,
Y ₁ and Y ₂ are each independently
(I) a hydrocarbon group (II) having 1 to 20 carbon atoms which may have an ether bond, a structure (I-II) containing a bond A and a bond B, and a polymerizable unsaturated group (I- III) in this order, or (II) a hydrocarbon group having 1 to 20 carbon atoms optionally having an ether bond (II-I), a structure containing a bond A or a bond B (II- II) and a structure containing one or more selected from the group consisting of polymerizable unsaturated groups (II-III),
at least one of Y ₁ and Y ₂ is (I);
Y ₁ and Y ₂ have a total number of polymerizable unsaturated groups of 4 or more,
bond A is one or more bonds selected from structural formulas (1) and (3);
Structural formula (1) is

and
Structural formula (3) is

and
Bond B is a urethane bond. ) Component (a-2) is selected from the group consisting of 2-mercaptoethanol, 3-mercapto-3-methyl-1-butanol, 1-mercapto-2-propanol, 3-mercapto-1-propanol and 1-thioglycerol or from diethanolamine, 2-piperidinemethanol, 2-piperidineethanol, 3-piperidinemethanol, 3-piperidineethanol, 4-piperidinemethanol, 4-piperidineethanol, 2-piperidinol, 3-piperidinol and 4-piperidinol One or more selected from the group consisting of
The group in which component (a-3) consists of 2-(meth)acryloyloxyethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate 2. A compound (a) according to claim 1 , which is one or more selected from Compound (a) according to claim 1 or 2 ,
Component (b) containing two or more (meth)acryloyl groups, and photopolymerization initiator (c)
An active energy ray-curable coating composition comprising: A release coating composition comprising the active energy ray-curable coating composition according to claim 3 . A laminate comprising a substrate and a cured product of the active energy ray-curable coating composition according to claim 3 or a cured product of the release coating composition according to claim 4 . A lamination comprising a step of curing with an active energy ray the active energy ray-curable coating composition according to claim 3 or the release coating composition according to claim 4 applied to at least one side of a substrate. body manufacturing method.