JP2022043002A - Compound, active energy ray-curable coating agent composition, release coating agent composition, laminate, and method for producing laminate - Google Patents

Abstract

To provide a compound that satisfactorily inhibits silicone migration, an active energy ray-curable coating agent composition containing the compound, a release coating agent composition, a laminate thereof, and a method for producing the laminate.SOLUTION: A compound is a reactant of a component containing a polymerizable unsaturated group and a polysiloxane (a-1), a component containing a thiol group and a hydroxy group and/or a component containing an amino group and a hydroxy group (a-2), and a component containing an isocyanate group and a polymerizable unsaturated group (a-3).SELECTED DRAWING: None

Description

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

Compounds containing polysiloxane can be added to resins and the like to have high hardness, flexibility, heat resistance, weather resistance, impact resistance, crack resistance, wear resistance, corrosion resistance, water resistance, water repellency, and electricity. It is possible to obtain a cured product having characteristics such as insulation and workability. Therefore, the compound containing polysiloxane is used in various fields such as a pressure-sensitive adhesive, a self-repairing coating agent, and a release coating agent. When a compound containing polysiloxane is used in applications such as a pressure-sensitive adhesive, a self-repairing coating agent, and a release coating agent, the component bleeds out on the surface of the coating film, and the pressure-sensitive adhesive further laminated on the coating film or the like. A compound containing polysiloxane was transferred to an adherend such as a resin molded product, and its properties were sometimes impaired.

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

As a result of diligent studies, the present inventor has found that the above-mentioned problems can be solved by using a predetermined 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 disclosure provides the following items:
(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).
The compound (a) according to the general formula (1), which is a reaction product of a component containing.
General formula (1):

(In general formula (1),
X ₁ to X ₂ and X ₅ to X ₆ are independently alkyl groups having 1 or more and 4 or less carbon atoms.
Each of X3 to _X4 is an alkyl group having 1 or more carbon atoms and ₄ or less carbon atoms, and may be the same or different for each repeating unit.
n is an integer of 1 or more and 400 or less.
Y ₁ and Y ₂ are independent of each other.
(I) A structure (I-II) containing a hydrocarbon group (I-I) 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-). A structure containing III) in this order, or a structure containing (II) a hydrocarbon group (II-I) having 1 or more and 20 or less carbon atoms which may have an ether bond, a bond A or a bond B (II-). It is a structure containing one or more selected from the group consisting of II) and a polymerizable unsaturated group (II-III).
At least one of Y ₁ and Y ₂ is (I),
The total number of polymerizable unsaturated groups of Y ₁ and Y ₂ is 4 or more.
Bond A is one or more bonds selected from the structural formulas (1) to (3).
Structural formula (1)

And
Structural formula (2)

And
Structural formula (3)

And
Bond B is a urethane bond. )
(Item 2)
(A-3) The compound (a) according to item 1, wherein the number of isocyanate groups in the component is one.
(Item 3)
(A-2) The component 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. One or more of the following or from diethanolamine, 2-piperidinethanol, 2-piperidinethanol, 3-piperidinmethanol, 3-piperidinethanol, 4-piperidinmethanol, 4-piperidinethanol, 2-piperidinol, 3-piperidinol and 4-piperidinol. One or more species selected from the group of
(A-3) A group consisting of 2- (meth) acryloyloxyethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate and 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate. The compound (a) according to item 1 or 2, which is one or more selected from the above.
(Item 4)
Compound (a) according to any one of items 1 to 3.
A component (b) containing two or more (meth) acryloyl groups, and a photopolymerization initiator (c).
An active energy ray-curable coating agent composition containing.
(Item 5)
A release coating agent composition containing the active energy ray-curable coating agent composition according to item 4.
(Item 6)
A laminate containing a substrate and a cured product of the active energy ray-curable coating agent composition according to item 4 or a cured product of the release coating agent composition according to item 5.
(Item 7)
A laminate comprising a step of curing the active energy ray-curable coating agent composition according to item 4 or the release coating agent composition according to item 5 coated on at least one surface of a substrate with active energy rays. Production method.

The compounds provided in the present disclosure can satisfactorily suppress silicone migration.

Throughout the present disclosure, the range of numerical values such as each physical property value and content can be appropriately set (for example, by selecting from the upper and lower limit values described in the following items). Specifically, for the numerical value φ, when the lower limit of the numerical value φ is exemplified by A1, A2, A3, etc. and the upper limit of the numerical value φ is exemplified by 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 to B1, A1 to B2, A1 to B3, A2 to B1, A2 to B2, A2 to B3, A3 to B1, A3 to B2, A3 to B3 Etc. are exemplified. In addition, in this disclosure, "-" is used in the sense that the numerical values described before and after it are included as the lower limit value and the upper limit value.

The compound (a) (also referred to as “component (a)” in the present disclosure) is a component (a-1) containing a polymerizable unsaturated group and a polysiloxane (in the present disclosure, “component (a-1)”. Also referred to as), a component containing a thiol group and a hydroxyl group and / or a component containing an amino group and a hydroxyl group (a-2) (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 sex unsaturated group (also referred to as “(a-3) component” in the present disclosure). The compound (a) thus obtained has a structure containing a polysiloxane, a structure containing a bond A and a bond B, and a structure containing a polymerizable unsaturated group.

<(a-1) component>
The component (a-1) is a component containing a polymerizable unsaturated group and a 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 to be done. Examples of the polymerizable unsaturated group include a structure containing a carbon-carbon double bond, a structure containing a carbon-carbon triple bond, and the like. Specific examples of the polymerizable unsaturated group include a vinyl group and a (meth) acryloyl group. As the component (a-1), the component of the general formula (2) is 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 independently alkyl groups having 1 or more carbon atoms and 4 or less carbon atoms.
χ ₃ to χ ₄ are independently alkyl groups having 1 or more and 4 or less carbon atoms, and may be the same or different for each repeating unit.
ψ ₁ to ψ ₂ are linear or branched hydrocarbon groups having 1 or more and 20 or less carbon atoms which may independently have an ether bond.
m is an integer of 1 or more and 400 or less.
ω ₁ to ω ₄ are independently hydrogen atoms or polymerizable unsaturated groups. )

The upper limit of the number of carbon atoms in χ ₁ to χ ₆ of the general formula (2) is independently exemplified by 4, 3, 2, etc., and the lower limit is exemplified by 3, 2, 1, etc. In one embodiment, the carbon numbers of χ ₁ to χ ₆ of the general formula (2) are preferably 1 or more and 4 or less independently of each other. As an alkyl group having 1 or more and 4 or less carbon atoms in χ ₁ to χ ₆ of the general formula (2), 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 group. Butyl groups are exemplified. That is, the alkyl groups having 1 to 4 carbon atoms of χ ₁ to χ ₆ may be linear or branched.

The "linear or branched hydrocarbon group having 1 or more and 20 or less carbon atoms which may have an ether bond" in ψ ₁ and ψ ₂ of the general formula (2) may have an ether bond. It refers to a linear hydrocarbon group having 1 to 20 carbon atoms or a branched hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond. The upper limit of the number of carbon atoms of ψ ₁ and ψ ₂ in the 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, etc. are exemplified. In one embodiment, the carbon atoms of ψ ₁ and ψ ₂ of the general formula (2) are preferably 1 or more and 20 or less independently of each other. As a linear or branched hydrocarbon group having 1 or more and 20 or less carbon atoms in ψ ₁ and ψ ₂ of the general formula (2), C _α H _2α-1 (α is an integer of 1 or more and 20 or less). The structure represented by is exemplified. Further, it may have an ester bond as well as an ether bond.

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

Of the ω ₁ to ω ₄ of the general formula (2), at least one is a polymerizable unsaturated group. Of ω ₁ to ω ₄ , those having a polymerizable unsaturated group are preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and even more preferably 1 or more and 2 or less. Is.

As a specific example of the component (a-1) represented by the general formula (2), a component containing a (meth) acryloyl group at both ends of the 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 Industry Co., Ltd.)), at the end of one polysiloxane (meth ) Ingredients containing acryloyl groups (product names "X-22-174ASX", "X-22-174BX", "KF-22", "X-22-2426", "X-22-2404" (Shinetsu Chemical Industry) (Manufactured by JNC Co., Ltd.)) (Product names "Silaplane FM-0711", "Silaplane FM-0721", "Silaplane FM-0725" (manufactured by JNC Co., Ltd.)) and the like are exemplified.

A component (a-1-1) containing a reactive functional group (for example, COOH group, etc.) and a polysiloxane (also referred to as “(a-1-1) component” in the present disclosure) and its reactive functional group. Reacting a functional group (for example, 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. Therefore, it is also possible to obtain the component (a-1). Examples of the reactive functional group include -OH group, -COOH group, -COOCO- group, -NCO group, -SH group, epoxy group, oxazoline group, amino group, polymerizable unsaturated group and the like. Examples of the amino group include a primary amino group (-NH ₂ ) and a secondary amino group (-NH-). As a combination of the reactive functional groups in the components (a-1-1) and (a-1-2), -OH group and -COOH group, amino group and polymerizable unsaturated group, -SH group and non-polymerizable group. Saturated groups, -OH groups and -NCO groups, amino groups and -NCO groups, -OH groups and -COOCO- groups and the like are exemplified.

Examples of the component (a-1-1) include those in which at least one of ω ₁ to ω ₄ of the general formula (2) is the above-mentioned reactive functional group. The component (a-1-1) may be a commercially available product. As the product, components containing amino groups at both ends of polysiloxane (product names "X-22-161A", "X-22-161B", "KF-8012", "KF-8008" (Shinetsu Chemical Industry Co., Ltd.) )), Ingredients containing epoxy groups at both ends of polysiloxane (product names "X-22-163", "X-22-163A", "X-22-163B", "X-22-163C" ( Shin-Etsu Chemical Industry Co., Ltd.), Ingredients containing -OH groups at both ends of polysiloxane (product names "KF-6000", "KF-6001", "KF-6002", "KF-6003" (Shin-Etsu Chemical) (Manufactured by 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 Ingredients (product name "X-22-167B", "X-22-167C" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.)), ingredients containing -COOH groups at both ends of polysiloxane (product name "X-22-" 162C "(manufactured by Shin-Etsu Chemical Industry Co., Ltd.), component containing an epoxy group at one end of polysiloxane (product name" X-22-173BX "," X-22-173DX "(manufactured by Shin-Etsu Chemical Industry Co., Ltd.) ), Components containing -OH group 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 Industry Co., Ltd.) (Product name" 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 the end of one polysiloxane (product name "X-22-3710" (Shinetsu Chemical Co., Ltd.) (Manufactured by Kogyo Co., Ltd.)), Ingredients 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 Industry Co., Ltd.) Product names" Silaplane FM-7711 "," Silaplane FM-7721 "," Silaplane FM-7725 "(manufactured by JNC Co., Ltd.), a component containing a (meth) acryloyl group at the end of one polysiloxane (product name" X-22-174ASX "," X-22-174BX " , "KF-22", "X-22-2426", "X-22-2404" (manufactured by Shin-Etsu Chemical Co., Ltd.) (Product name "Silaplane FM-0711", "Silaplane FM-0721" , "Cyraplane FM-0725" (manufactured by JNC Co., Ltd.) and the like are exemplified.

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

(A-1-1) The upper limit of the number average molecular weight of the components 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, 16,000, 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, 8,000, 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. are exemplified, 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, 15,000, 15,000, 14,000, 14,000, 13,500, 13,000, 12,500, 12,000, 11,500, 11,000, 10,500, 10, 000, 9,500, 9,000, 8,000, 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 the component (a-1-1) is preferably about 1,000 to 20,000. When the number average molecular weight of the component (a-1-1) is equal to or higher than the above lower limit, it is considered that the composition containing the compound (a) of the present disclosure tends to have excellent light peelability when used as a peeling layer. There is. It is considered that the light peelability tends to be better as the number average molecular weight of the component (a-1-1) is higher. On the other hand, it is considered that the lower the number average molecular weight of the component (a-1-1) is, the better the silicone migration can be suppressed. In the present disclosure, the number average molecular weight is a polystyrene-equivalent value obtained by a gel permeation chromatography method.

The upper limit of the functional group equivalent (g / mol) of the 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 and the like are exemplified. , 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 the component (a-1-1) is preferably about 1,000 to 20,000. When the functional group equivalent (g / mol) of the component (a-1-1) is equal to or higher than the above lower limit, the composition containing the compound (a) of the present disclosure tends to be excellent in light peelability when used as a peeling layer. I think it is in. It is considered that the light peelability tends to be improved as the functional group equivalent (g / mol) of the component (a-1-1) is higher. On the other hand, it is considered that the lower the functional group equivalent (g / mol) of the component (a-1-1) is, the better the silicone migration can be suppressed. In the present disclosure, the functional group equivalent is the molecular weight per functional group.

(A-1) The upper limit of the content (solid content conversion) of the component (a-1-1) in the total 100% by mass (solid content conversion) of the components constituting the component is 99, 98, 97, 96, 95, 94, 93, 92, 91, 90, 85, 80, 75, 70, 65, 60, 55% by mass and the like are exemplified, and the lower limit is 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 (solid content equivalent) of the component (a-1-1) in the total 100% by mass (solid content equivalent) of the components constituting the component (a-1) is 50 to 99 mass. % Is preferable.

As the component (a-1-2), a component containing an -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, and the like. -A component containing an 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, Examples of components include an amino group and a polymerizable unsaturated group. -As a component containing an OH group and a polymerizable unsaturated group, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, (meth). ) 2-Hydroxy-3-phenoxypropyl acrylate, glycerindi (meth) acrylate, 2-hydroxy-3- (meth) acryloyl-oxypropyl (meth) acrylate, 1-((meth) acryloyloxy) -3-( Examples thereof include (meth) acryloyloxy-2-propanol, pentaelthritol tri (meth) acrylate, dipentaelthritol tetra (meth) acrylate, tripentaelsritol hepta (meth) acrylate, and the like. Examples of the component containing the polymerizable unsaturated group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl phthalic acid, mono succinate (2- (meth) acryloyloxyethyl) and the like. -As a component containing a group and a polymerizable unsaturated group, anhydrous (meth) acrylic acid, anhydrous crotonic acid, anhydrous maleic acid, anhydrous itaconic acid, anhydrous isocyanate, and the like are exemplified.-NCO group and polymerizable unsaturated group. As components containing, 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 (meth) acrylate (3,4-epoxycyclohexyl) methyl, glycidyl (meth) acrylate, and allylglycidyl ether. Examples of the component 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. As a component containing an amino group and a polymerizable unsaturated group, 3-amino-1-propene, 3-amino-2-methyl-1-propene, 2- (2-propynyloxy) ethylamine, diallylamine, di (2). -Propinyl) amine, 1,1-dimethyl-2-propinylamine, aminophenylacetylene, vinylaniline, N-tert-butylallylamine, oleylamine and the like are exemplified.

Commercially available products may be used as the component (a-1-2). The products include 2-hydroxyethyl (meth) acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 4-hydroxybutyl (meth) acrylate (manufactured by Mitsubishi Chemical Co., Ltd.), and (meth) acrylic acid 3-hydroxy-1-. Adamanthyl (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 2-hydroxy-3-phenoxypropyl (meth) acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 2- (meth) acryloyloxyethyl phthalic acid (Shin-Nakamura Chemical Industry Co., Ltd.) (Manufactured by Tokyo Kasei Kogyo Co., Ltd.), Mono (2- (meth) acryloyloxyethyl) (manufactured by Tokyo Kasei Kogyo 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") , "Blemmer GAM-R", manufactured by Nichiyu Co., Ltd.), diallylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and the like.

The substance exemplified as the component (a-1-2) and the known component (a-1-2) can be used alone or in combination of two or more. The 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, and 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, and even more preferably one selected from maleic anhydride, itaconic anhydride and citraconic anhydride. And / or one selected from 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethyloxyethyl isocyanate and 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate. Yes, particularly preferred are maleic anhydride, 2- (meth) acryloyloxyethyl isocyanate, and / or 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate.

The upper limit of the molecular weight of the component (a-1-2) is 1,000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, Examples are 150, 100, etc., and the lower limit is 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, etc. Illustrated. In one embodiment, the molecular weight of the 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.

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

The upper limit of the mass ratio of the solid content of the (a-1-1) component and the (a-1-2) component ((a-1-1) component / (a-1-2) component) 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 limit 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, 50/50 and the like are exemplified. In one embodiment, the mass ratio of the solid content of the (a-1-1) component and the (a-1-2) component ((a-1-1) component / (a-1-2) component) is determined. It is preferably about 50/50 to 99/1.

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

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

(A-1) The upper limit of the number average molecular weight of the components 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, Examples include 6,000, 5,500, 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, 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, 8,000, 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 the component (a-1) is preferably about 1,000 to 20,000. When the number average molecular weight of the component (a-1) is equal to or higher than the above lower limit, it is considered that the composition containing the compound (a) of the present disclosure tends to have excellent light peelability when used as a peeling layer. It is considered that the light peelability tends to be better as the number average molecular weight of the component (a-1) is higher. On the other hand, it is considered that the lower the number average molecular weight of the component (a-1) is, the better the silicone migration can be suppressed. In the present disclosure, the number average molecular weight is a polystyrene-equivalent value obtained by a gel permeation chromatography method.

The upper limit of the functional group equivalent (g / mol) of the 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, 8,000, 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. 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, 8,000, 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 the component (a-1) is preferably about 1,000 to 20,000. When the functional group equivalent (g / mol) of the component (a-1) is equal to or higher than the above lower limit, the composition containing the compound (a) of the present disclosure tends to be excellent in light peelability when used as a peeling layer. I believe. It is considered that the light peelability tends to be improved as the functional group equivalent (g / mol) of the component (a-1) is higher. On the other hand, it is considered that the lower the functional group equivalent (g / mol) of the component (a-1) is, the better the silicone migration can be suppressed. In the present disclosure, the functional group equivalent is the molecular weight per functional group. Further, the polymerizable unsaturated group which is the functional group of the component (a-1) may be located at both ends or one end of the polysiloxane chain.

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

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

<(a-2) component>
The 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, or the like.

As a component containing a thiol group and a hydroxyl group, 2-mercaptoethanol, 3-mercapto-3-methyl-1-butanol, 1-mercapto-2-propanol, 3-mercapto-1-propanol, 2-hydroxybenzenethiol, 4- Examples thereof include mercaptophenol, 2-mercaptohydroquinone, 11-mercaptoundecylhydroquinone, 2,3-dimercaptopropanol, 1-thioglycerol, dithiotreitol and the like. The component containing a thiol group and a hydroxyl group may be synthesized by various known methods. As a method for synthesizing a component containing a thiol group and a hydroxyl group, a reaction between hydrogen sulfide ( _H2S ) and an epoxide is exemplified. As epoxides, 1-butoxy-2,3-epoxypropane, 1,2-epoxybutane, 1-tert-butoxy-2,3-epoxypropane, 1-dodecene epoxide, 1,2-octylene oxide, 1, Examples thereof include 2-pentylene oxide and cyclopentene oxide.

As components containing amino groups and hydroxyl groups, 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-aminopropane-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-piperidinmethanol, 2-piperidinethanol, 3-piperidinethanol, 3-piperidinethanol, 4-piperidinethanol, 4-piperidinethanol, 2-piperidinol, 3-piperidinol, 4-piperidinol, etc. Illustrated.

The substance exemplified as the component (a-2) and the known component (a-2) can be used alone or in combination of two or more. The 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, and 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-piperidinmethanol, 2-piperidinethanol, 3-piperidinmethanol, 3-piperidinethanol , 4-Piperidinmethanol, 4-Piperidinethanol, 2-piperidinol, 3-piperidinol and 4-piperidinol, one or more selected from the group, and particularly preferably 1-thioglycerol or diethanolamine. Since the solvent resistance is particularly good, the component (a-2) containing a thiol group and a hydroxyl group is better than the component containing an amino group and a hydroxyl group.

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

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

(A-2) The upper limit of the number of hydroxyl groups in the component is 10, 9, 8, 7, 6, 5, 4, 3, 2, etc., and the lower limit is 9, 8, 7, 6, 5, etc. 4, 3, 2, 1, etc. are exemplified. In one embodiment, the number of hydroxyl groups in the component (a-2) is preferably 1 or more and 10 or less. (A-2) The upper limit of the number of thiol groups or amino groups in the component 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 thiol groups or amino groups in the component (a-2) is preferably 1 or more and 10 or less. The number of thiol groups or amino groups in the component (a-2) is particularly preferably one because the peeling is lightened.

The upper limit of the mass ratio of the solid content of the component (a-1) and the component (a-2) (component (a-1) / component (a-2)) is 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. are exemplified, 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 etc. are exemplified. In one embodiment, the mass ratio of the solid content of the component (a-1) and the component (a-2) (component (a-1) / component (a-2)) is 75/25 to 99.5 /. About 0.5 is preferable.

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

<(a-3) component>
The 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 linear shape, a branched shape, or the like.

As the component (a-3), 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. The component (a-3) is a component having two or more isocyanate groups (a-3-1), a functional group that reacts with the isocyanate group (for example, an OH group), and a component having a polymerizable unsaturated group (a-3). It may be obtained by reacting with -2). Examples of such component (a-3) include hexamethylene diisocyanate or half urethane of isophorone diisocyanate and hydroxyethyl (meth) acrylate.

The substance exemplified as the component (a-3) and the known component (a-3) can be used alone or in combination of two or more. The components (a-3) are 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 isocyanate, preferably 2- (meth) acryloyloxyethyl isocyanate and / or 1,1- (bis (meth) acryloyloxymethyl) ethyl. Isocyanate.

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

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

(A-3) The upper limit of the number of isocyanate groups in the component 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 the component (a-3) is preferably 1 or more and 10 or less. The number of isocyanate groups in the component (a-3) is most preferably one because peeling is lightened. (A-3) The upper limit of the number of polymerizable unsaturated groups in the component 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 polymerizable unsaturated groups in the component (a-3) is preferably 1 or more and 10 or less.

The upper limit of the mass ratio of the solid content of the component (a-1) and the component (a-3) (component (a-1) / component (a-3)) is 99/1, 95/5, 90/10, 85/15, 80/20, 75/25 and the like are exemplified, and the lower limit is 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 the component (a-1) and the component (a-3) (component (a-1) / component (a-3)) is about 70/30 to 99/1. Is preferable.

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

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

<Other ingredients>
As a component constituting the compound (a), a component (a-4) other than the component (a-1), the component (a-2), and the component (a-3) may be used. Examples of the component (a-4) include a component (a-1), a component (a-2), and a component having a functional group that reacts with the functional group of the component (a-3). The component (a-4) may be reacted with any of the components (a-1), (a-2), and (a-3). When, for example, a component having a trifunctional or higher isocyanate group is used as the component (a-4), peeling tends to be heavy, so it is preferable not to use a component having a trifunctional or higher functional isocyanate group. Further, it is conceivable to use the component (a-4) as a component when synthesizing the component (a-1), but for the same reason as described above, do not use a component having a trifunctional or higher isocyanate group. Is preferable. It is considered that this is due to the fact that the mass ratio of the polysiloxane portion is lower than that when the component having an isocyanate group less than trifunctional is used due to the component having a trifunctional or higher functional isocyanate group. There is.

<Compound (a)>
The compound (a) of the present disclosure has a structure of the 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 independently alkyl groups having 1 or more and 4 or less carbon atoms.
Each of X3 to _X4 is an alkyl group having 1 or more carbon atoms and ₄ or less carbon atoms, and may be the same or different for each repeating unit.
n is an integer of 1 or more and 400 or less.
Y ₁ and Y ₂ are independent of each other.
(I) A structure (I-II) containing a hydrocarbon group (I-I) having 1 or more and 20 or less carbon atoms which may have an ether bond, a bond A and a bond B, and a polymerizable unsaturated group (I-). A structure containing III) in this order, or a structure containing (II) a hydrocarbon group (II-I) having 1 or more and 20 or less carbon atoms which may have an ether bond, a bond A or a bond B (II-). It is a structure containing one or more selected from the group consisting of II) and a polymerizable unsaturated group (II-III).
At least one of Y ₁ and Y ₂ is (I),
The total number of polymerizable unsaturated groups of Y ₁ and Y ₂ is 4 or more.
Bond A is one or more bonds selected from the structural formulas (1) to (3).
Structural formula (1)

And
Structural formula (2)

And
Structural formula (3)

And
Bond B is a urethane bond. )

The upper limit of the number of carbon atoms of X1 to X6 in the general _formula ( ₁ ) is independently exemplified by 4, 3, 2, etc., and the lower limit is exemplified by 3, 2, 1, etc. In one embodiment, the carbon atoms of X ₁ to X ₆ of the general formula (1) are preferably 1 or more and 4 or less independently of each other. As the alkyl group having 1 or more and 4 or less carbon atoms of X ₁ to X ₆ of the general formula (1), 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 group. Butyl groups are exemplified. That is, the alkyl groups of X ₁ to X ₆ having 1 or more and 4 or less carbon atoms may be linear or branched.

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

The "hydrocarbon groups having 1 or more and 20 or less carbon atoms which may have an ether bond" of Y ₁ and Y ₂ of the general formula (1) may be linear or branched, respectively. good. The upper limits of the carbon number of "hydrocarbon groups having 1 or more and ₂₀ or less carbon atoms which may have an ether bond" of Y1 and Y2 of the general formula ( ₁ ) are independently set to 20, 18, and 16, respectively. 14, 12, 10, 8, 6, 4, 2, etc. are exemplified, and the lower limit is 18, 16, 14, 12, 10, 8, 6, 4, 2, 1, etc. are exemplified. In one embodiment, the carbon numbers of Y ₁ and Y ₂ of the general formula (1) of "hydrocarbon groups having 1 or more and 20 or less carbon atoms which may have an ether bond" are independently 1 or more. It is preferably about 20 or less. C _β H _{2β + 1 ,} C _β H _2β , or C _β H _{2β-1 (} β is a hydrocarbon group having 1 or more and 20 or less carbon atoms in (I)) of the general formula (1). An integer of 1 or more and 20 or less) is exemplified. At least one of Y ₁ and Y ₂ of the general formula (1) is (I). Further, it may have an ester bond as well as an ether bond.

The upper limit of the number of polymerizable unsaturated groups of Y ₁ and Y ₂ of 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 and the like are exemplified. The lower limit is 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, etc. are exemplified. In one embodiment, the number of polymerizable unsaturated groups of Y ₁ and Y ₂ of the general formula (1) of the compound (a) is 4 or more, preferably about 4 to 64.

Y1 and / or Y2 of the general formula ( ₁ ) of the compound (a) "bond A and bond B to a hydrocarbon group (I-I) having 1 to ₂₀ carbon atoms which may have an ether bond". The "structure containing the structure (I-II) containing the hydrocarbon and the polymerizable unsaturated group (I-III) in this order" means "a structure having an ether bond in the order of proximity to the polysiloxane chain". It means "a structure containing 20 or less hydrocarbon groups (I-I), a structure (I-II) containing a bond A and a bond B, and a polymerizable unsaturated group (I-III) in this order". The compound (a) contains a hydrocarbon group (II-I) having 1 or more and 20 or less carbon atoms, a bond A or a bond B, which may have an ether bond, of Y ₁ or Y ₂ of the general formula (1). The "structure containing one or more selected from the group consisting of the structure (II-II) and the polymerizable unsaturated group (II-III)" is preferably "a structure having one or more carbon atoms which may have an ether bond". A structure (II-) containing a hydrocarbon group (II-I) having 20 or less carbon atoms and a hydrocarbon group (II-I) having 1 or more and 20 or less carbon atoms which may have an ether bond and a bond A or a bond B. "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 structure containing A or a bond B (II-II) and a polymerizable unsaturated group (II-III) "or" a hydrocarbon group having 1 or more and 20 or less carbon atoms which may have an ether bond. It is one of "a structure containing (II-I) and a structure containing a bond A or a bond B (II-II) and a polymerizable unsaturated group (II-III)", and more preferably "having an ether bond". Hydrocarbon groups having 1 or more and 20 or less carbon atoms (II-I) which may be present, and "hydrocarbon groups having 1 or more and 20 or less carbon atoms which may have ether bonds in order of proximity to the polysiloxane chain (II). A structure containing —I) and a structure containing bond A or bond B (II-II) in this order ”,“ in order from the polysiloxane chain, the number of carbon atoms may be 1 or more and 20 or less, which may have an ether bond. 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 order from the polysiloxane chain (II-II). "Structure containing a polymerizable unsaturated group (II-III) in this order", "A hydrocarbon group having 1 or more and 20 or less carbon atoms which may have an ether bond in order from the polysiloxane chain" (II- It is one of "a structure containing I) and a structure (II-II) containing a bond A or a bond B and a polymerizable unsaturated group (II-III) in this order.

When at least one of the component (a-2), the component (a-3), and the component (a-1-2) used as needed is a branched structure, the general formula (a) of the compound (a) ( In 1), the structures of the general formula (3) and / or the general formula (4) may be included. The structure of the general formula (1) of the compound (a) of the present disclosure may be linear, partially linear, branched, or partially branched. .. It is considered that the smaller the number of branches, the more the composition containing the compound (a) of the present disclosure tends to be lightly peeled, and the larger the number of branches, the better the silicone migration can be suppressed. I think there is a tendency.

（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 or more and 50 or less carbon atoms.
p is an integer of 1 or more and 20 or less,
The line is a bond of the general formula (1) to (I-I) or (II-I), a bond of the general formula (1) to a further unit of (I-II) or (II-II), or general. It is a binding to (I-III) or (II-III) of the formula (1). )

The “linear or branched hydrocarbon group having 1 or more and 50 or less carbon atoms” in (V) of the general formula (3) is a linear hydrocarbon group having 1 or more and 50 or less carbon atoms or 1 or more and 50 carbon atoms. Refers to the following branched hydrocarbon groups. The upper limit of the number of carbon atoms in (V) of the general formula (3) is 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc. , And the lower limit is 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, and the like. In one embodiment, the carbon number of (V) in the general formula (3) is preferably 1 or more and 50 or less. As a linear or branched hydrocarbon group having 1 or more and 50 or less carbon atoms in (V) of the general formula (3), it is represented by C _δ H _2δ-1 (δ is an integer of 1 or more and 50 or less). The structure to be used is 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 general formula (4),
(Iv) is bond A or bond B,
(V) and (v)'are independently linear or branched hydrocarbon groups having 1 or more and 25 or less carbon atoms.
p is an integer of 1 or more and 20 or less,
The line is a bond of the general formula (1) to (I-I) or (II-I), a bond of the general formula (1) to a further unit of (I-II) or (II-II), or general. It is a binding to (I-III) or (II-III) of the formula (1). )

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

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

Compound (a) is a reaction product of a component containing (a-1) component, (a-2) component, and (a-3) component. The method for synthesizing the compound (a) is not particularly limited, but it is conceivable to react in the order described below. In the reaction, it is also conceivable to obtain the compound (a) in which the reaction does not partially proceed by taking a method such as adjusting the number of moles of each component (the functional group possessed by the component).
(1) Method of reacting the component (a-1) and the component (a-2) and then the component (a-3) (2) The component (a-1) and the component (a-2) After reacting with the components, the (a-3) component is reacted, then the (a-2) component is reacted, and the (a-3) component is further reacted with the (3) and (a-1) components. After reacting with the component (a-2), the component (a-3) is reacted, then the component (a-2) is reacted, the component (a-3) is further reacted, and then (a) is further reacted. -2) A method of reacting the components and finally (a-3) the components.

Of the above synthetic methods for compound (a), in (1), bond A-bond B is formed in this order, and in (2), bond A-bond B-bond A-bond B is formed in this order. In 3), the bonds A-bond B-bond A-bond B-bond A-bond B are formed in this order. When the component (a-1) contains the bond B, the bond B-bond A-bond B is formed in this order in (1), and the bond B-bond A-bond B-bond A is formed 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, the general formula (5) is exemplified as the arrangement order of the bond A and the bond B having the structure including the bond A and the bond B of the compound (a) of the present disclosure.

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

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

Of the bonds of the compound (a), the bond A (that is, one or more bonds selected from the structural formulas (1) to (3)) is, for example, a thiol group or an amino group in the component (a-2). It is obtained by proceeding with a reaction with a polymerizable unsaturated group in the component (a-1) or the component (a-3). In the reaction, for example, it is possible to react in the presence of a catalyst at a specific temperature. The specific temperature is preferably about 50 to 120 ° C, more preferably 60 to 100 ° C. Further, the bond B (that is, the urethane bond) is obtained, for example, by reacting the hydroxyl group of the component (a-2) with the isocyanate group of the component (a-3). In the reaction, for example, it is possible to react in the presence of a catalyst at a specific temperature. The specific temperature is preferably about 50 to 120 ° C, more preferably 60 to 100 ° C. As the solvent at the time of these reactions, one or more selected from a ketone solvent, an aromatic solvent and an ester solvent are preferably used.

(A) The upper limit of the number average molecular weight of the components 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. are exemplified, 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 the component (a) is preferably about 1,000 to 50,000.

Examples of the compound (a) of the present disclosure include chemical 16 to chemical 19 and the like. Chemical formula 16 has eight functionalities on one end on the right side, chemical 17 has eight functionalities on one end on the right side, and bifunctionality on one terminal on the left side, and chemical 18 has eight functionalities on one end on the right side and one on the left side. It has 5 functionalities at the ends and the chemical 19 has 8 functionalities at both ends.

<Ingredients that can be used in combination with compound (a)>
Since the compound (a) of the present disclosure contains four or more polymerizable unsaturated groups, it is conceivable to use the compound (a) in a conventionally known situation in which a polymerizable unsaturated group is used. For example, a component (a component containing two or more (meth) acryloyl groups, a component containing a thiol group (SH group), an initiator, a component applied when performing various polymerizations with respect to the compound (a) of the present disclosure. It is conceivable to use it by adding an organic solvent, etc.). Among 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) and the like are shown in detail. In the present disclosure, the composition containing the component (a), the component (b), and the component (c) is also referred to as an active energy ray-curable coating agent composition. Further, the active energy ray-curable coating agent composition of the present disclosure is particularly preferable to be used as a release coating agent composition because it is excellent in light peelability and the like.

The upper limit of the content (solid content equivalent) of the component (a) in the total 100% by mass (solid content equivalent) of the component (a), the component (b) and the component (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 limit is 40, 30, 20, 10, 8, 6, 4, 2, 1.8, 1.6, 1.4, 1.2, 1.0, 0.8, 0. 6.6, 0.4, 0.2, 0.1, 0.05% by mass and the like are exemplified. In one embodiment, the range of the content (solid content equivalent) of the component (a) in the total 100% by mass (solid content equivalent) of the component (a), the component (b) and the component (c) is 0.05. It is preferably about 10% by mass.

<Component (b) containing two or more (meth) acryloyl groups>
A compound having a chain structure and having two or more (meth) acryloyl groups as a component (b) containing two or more (meth) acryloyl groups (also referred to as “component (b)” in the present disclosure). , 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 are exemplified. In the present disclosure, the chain structure refers to a structure having no cyclic structure, and may be linear or include a branched structure.

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

As a compound having a chain structure and having two or more (meth) acryloyl groups, a di (meth) acrylate having a chain structure, a tri (meth) acrylate having a chain structure, and a tetra (meth) having a chain structure. ) Acrylate, penta (meth) acrylate having a chain structure, hexa (meth) acrylate having a chain structure, and the like are exemplified.

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

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

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

Examples of the penta (meth) acrylate having a chain structure include dipentaerythritol penta (meth) acrylate.

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

Examples of other (meth) acrylates having a chain structure include 16-20 functional acrylates having a dendrimer structure (product name “Siris-501”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

Examples of the compound having an alicyclic hydrocarbon group and having two or more (meth) acryloyl groups include di (meth) acrylate having an alicyclic hydrocarbon group.

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

Examples of the compound having an aromatic hydrocarbon group and having two or more (meth) acryloyl groups include di (meth) acrylate having an aromatic hydrocarbon group.

As di (meth) acrylates having an aromatic hydrocarbon group, bisphenol A di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, bis (meth) acrylic acid [3,3'-[isopropyridenebis (p-phenyleneoxy)] bis (2-hydroxypropane)]-1,1'-diyl, bisphenol A diglycidyl ether (meth) acrylic acid adduct and the like are exemplified. .. The (meth) acrylic acid is methacrylic acid and / or acrylic acid.

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

Examples of other components containing two or more (meth) acryloyl groups include polyurethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate.

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

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

Examples of the polyether polyol include polyalkylene glycol (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.) and the like. Commercially available products may be used as the polyether polyol. Examples of the product include product names "ADEKApolyether P series", "ADEKApolyether G series", "ADEKApolyether EDP series" (manufactured by ADEKA Corporation) and the like.

As a polyester polyol, one obtained by reacting a polyol with a polycarboxylic acid (succinic acid, phthalic acid, malonic acid, maleic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, etc.), a cyclic ester (propiolactone, Examples thereof include a ring-opening polymer of β-methyl-δ-valerolactone, ε-caprolactone, etc., and a tripartite reaction product of a polyol, a polycarboxylic acid, and a cyclic ester. Commercially available products may be used as the polyester polyol. The products include the product names "Kuraray Polyol P Series" and "Kuraray Polyol F Series" (manufactured by Kuraray Co., Ltd.), the product name "Plaxel 205" (manufactured by Daicel Corporation), and the product name "Polylite OD-X-2155". "(Manufactured by DIC Corporation) and the like are exemplified.

Examples of the polycarbonate polyol include a reaction product of the polyol and phosgene, a ring-opening polymer of a cyclic carbonate ester (alkylene carbonate, etc.), and the like. Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate and the like. Commercially available products may be used as the polycarbonate polyol. Examples of the product include the product name "Kuraray Polyol C Series" (manufactured by Kuraray Co., Ltd.).

Examples of the acrylic polyol include a homopolymer or a copolymer of an acrylic monomer containing one or more hydroxyl groups in one molecule, or a copolymer of the copolymer with another monomer. .. Commercially available products may be used as the acrylic polyol. Examples of the product include the product name "ARUFON UH-2000 series" (manufactured by Toagosei Co., Ltd.).

Examples of the polyolefin polyol include polybutadiene containing two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorinated products thereof. Commercially available products may be used as the polyolefin polyol. Examples of the product include the product name "NISSO-PB GI series" (manufactured by Nippon Soda Corporation).

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

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

Examples of the isocyanate group-containing (meth) acrylate include 2- (meth) acryloyloxyethyl isocyanate and 1,1- (bisacryloyloxymethyl) ethyl isocyanate. A substance exemplified as an isocyanate group-containing (meth) acrylate and a known isocyanate group-containing (meth) acrylate can be used alone or in combination of two or more.

Various known methods are exemplified as a method for synthesizing polyester (meth) acrylate. Various known synthetic methods for polyester (meth) acrylates include (1) carboxyl group-containing (meth) acrylates (carboxyethyl (meth) acrylates and carboxypolycaprolactones) in hydroxyl group-terminated polyesters obtained by reacting polycarboxylic acids with polyols. Method of reacting 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 with a polyol is exemplified.
In these methods, it is conceivable to appropriately use various known catalysts as needed.

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

Commercially available products may be used for the components containing two or more (meth) acryloyl groups. As the product, pentaerythritol triacrylate ((product name "A-TMM-3", "A-TMM-3L", manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), (product name "Miramer M301", manufactured by MIWON)) , (Product name "Aronix M-309", manufactured by Toa Synthetic Co., Ltd.), Ditrimethylol propanetetraacrylate (Product name "Aronix M-408", manufactured by Toa Synthetic Co., Ltd.), Pentaerythritol tetra ethoxylated (Meta) ) 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 Industry Co., Ltd.), (Product names "Aronix M-403", "Aronix M-400", "Aronix M-402", "Aronix M-404", "Aronix M-405", "Aronix M-406", Toa Synthetic Co., Ltd. )), Tripentaerythritol poly (meth) acrylate (product name "Viscoat # 802, TriPEA", manufactured by Osaka Organic Chemical Industry Co., Ltd.), polyfunctional acrylate including dendrimer structure (product name "Siris-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 Co., Ltd.) , (Product name "DPHA40H", "UX5003", manufactured by Nippon Kayaku Co., Ltd.), (Product name "Beamset 577", manufactured by Arakawa Chemical Industry Co., Ltd.), (Product name "8UX-015A", Taisei Fine Chemicals (Manufactured by Co., Ltd.), (Product name "U15HA", manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), (Product name "Miramer PU610", manufactured by Miwon Specialty Chemical) (Product name "Etercure 6196-100", Eternal Materials) ), Bisphenol A type epoxy acrylate (product name "Aronix OT-2501", manufactured by Toa Synthetic Co., Ltd.) and the like are exemplified.

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. ..

The component containing two or more (meth) acryloyl groups is easy to cure even when the dose of the active energy ray is lowered, and the peelability when the composition of the present disclosure is used as the release layer is also good. It is preferably a compound containing a hydroxyl group and containing 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, and even 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 number of carbon atoms of the component containing two or more (meth) acryloyl groups is exemplified by 200, 150, 100, 80, 60, 50, 40, 30, 20, 10 and the like, and the lower limit is 100, 80. Examples include 60, 50, 40, 30, 20, 10, 8, 6, 4, and the like. In one embodiment, the carbon number of 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 a component containing two or more (meth) acryloyl groups is 30, 25, 20, 18, 16, 15, 10, 8, 6, 5, 4, 3, etc. Is exemplified, and the lower limit is 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. The lower limit is 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 the component (b) is preferably about 50 to 5,000.

The upper limit of the mass ratio of the solid content of the component (a) and the component (b) (component (a) / component (b)) is 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. are exemplified, and the lower limit is 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 are exemplified. In one embodiment, the mass ratio of the solid content of the component (a) and the component (b) (component (a) / component (b)) is preferably about 0.1 / 99.9 to 50/50.

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

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

Examples of the radical-based photopolymerization initiator include an alkylphenone-type photopolymerization initiator, an acylphosphine oxide-type photopolymerization initiator, a hydrogen-drawing-type photopolymerization initiator, and an oxime ester-type photopolymerization initiator.

As an alkylphenone-type photopolymerization initiator, benzyldimethyl ketal such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- 2-Methyl-1-propane-1-one, 2-hirodoxy-1-{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one , Α-Hydroxyalkylphenone such as 1-hydroxycyclohexylphenylketone, α-aminoalkylphenone such as 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like are exemplified. Benzyl.

Examples of the acylphosphine oxide type photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide and the like.

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

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

As a cationic photopolymerization initiator, a mixture of iodonium, (4-methylphenyl)] 4- (2-methylpropyl) phenyl] -hexafluorophosphate (1-) and propylene carbonate, triarylsulfonium hexafluorophosphate, Examples thereof include triarylsulphonium tetrakis- (pentafluorophenyl) borate and the like.

Examples of the anionic photopolymerization initiator include cobalt amine-based complexes, o-nitrobenzyl alcohol carbamic acid esters, and oxime esters.

The photopolymerization initiator is preferably a radical-based photopolymerization initiator because of its excellent curing rate, more preferably an alkylphenylone-type photopolymerization initiator, and further preferably α-aminoalkylphenone and / or α-hydroxy. Alkylphenone, particularly preferably 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-). Methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, and one or more selected from 1-hydroxycyclohexylphenylketone.

Commercially available products may be used as the photopolymerization initiator. The products include 2,2-dimethoxy-1,2-diphenylethane-1-one (product name "Omnirad" (hereinafter, also referred to as "Omnirad") 651 ", manufactured by IGM Resins), 1- [4- (4). 2-Hydroxyethoxy) -Phenyl] -2-Hydroxy-2-methyl-1-propane-1-one (product name "Omnirad 2959", manufactured by IGM Resins), 2-Hirodoxy-1- {4- [4- [4- [4-] (2-Hydroxy-2-methyl-propionyl) -benzyl] Phenyl} -2-methyl-propane-1-one (product name "Omnirad 127", manufactured by IGM Resins), 2-methyl-1- (4-methylthio) Phenyl) -2-morpholinopropane-1-one (product name "Omnirad 907", manufactured by IGM Resins), 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide (product name "Omnirad TPO H", IGM) (Resins), Bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide (Product name "Omnirad 819", IGM Resins), Phenylglycylic acid methyl ester (Product name "Omnirad MBF", IGM Resins), 1,2-octanedione, 1- [4- (Phenylthio)-, 2- (O-benzoyloxime)] (Product name "IRGACURE OXE 01", BASF Japan Co., Ltd.), Etanon , 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-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 ”, IGM Resins), Triarylsulfonium HexafluoroPhosphate (Product name“ Omnicat 270 ”, IGM Resins), Triarylsulfonium tetrakis- (pentafluorophenyl) borate (Product name“ IRGACURE 290 ”) , BASF Japan Co., Ltd.) and the like are exemplified.

The substance exemplified as the photopolymerization initiator and the known photopolymerization initiator can be used alone or in combination of two or more.

The upper limit of the mass ratio of the solid content of the component (a) and the component (c) (component (a) / component (c)) is 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 limit is 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. Illustrated. In one embodiment, the mass ratio of the solid content of the component (a) and the component (c) (component (a) / component (c)) is preferably about 1/99 to 70/30.

The upper limit of the mass ratio of the solid content of the component (b) and the component (c) (component (b) / component (c)) is 99/1, 95/5, 90/10, 85/15, 80/20, 75/25 and the like are exemplified, and the lower limit is 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 the component (b) and the component (c) (component (b) / component (c)) is preferably about 70/30 to 99/1.

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

<Other agents that can be blended>
Further, the compound (a) of the present disclosure includes a binder resin (acrylic resin, urethane resin, polyester resin, epoxy resin, alkyd resin, etc.) other than the components exemplified above, an antislip agent, a slip agent, and a preservative, if necessary. , Various additives such as rust preventives, pH adjusters, pigments, dyes, lubricants, leveling agents, catalysts, defoaming agents, photosensitizers (amines, quinones, etc.) can also be blended. It is also conceivable to add an antioxidant such as hindered amine, an amine-containing compound such as triethanolamine, and a component containing a thiol group (SH group). The component containing a thiol group (SH group) may be added to the composition containing the compound (a) of the present disclosure in order to cure the composition containing the compound (a) of the present disclosure by a thiol / ene reaction. Be done. As a component containing a thiol group (SH group), various known substances can be used alone or in combination of two or more. For example, a component containing a thiol group (SH group) described in JP2013-231167 and a component containing a thiol group (SH group) described in JP2013-213200A are exemplified.

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

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

Examples of the aromatic solvent include toluene, xylene and the like.

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

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

As glycol ether solvents, 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 thereof 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, and ethylene glycol mono-t-butyl ether.

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 the petroleum-based solvent include Solbesso # 100 (manufactured by Exxon Co., Ltd.) and Solbesso # 150 (manufactured by Exxon Co., Ltd.).

Chloroform and the like are exemplified as the haloalkane solvent.

Examples of the amide solvent include dimethylformamide and the like.

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

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

Examples of the base material on which the composition of the present disclosure is applied include a glass base material, a metal base material, a plastic base material, and the like. Examples of the plastic base material include a thermoplastic base material, a thermosetting plastic base material, and the like. Examples of the thermoplastic plastic base material include general-purpose plastic base materials and engineering plastic base materials. Examples of the general-purpose plastic base material include olefin-based, polyester-based, acrylic-based, vinyl-based, and polystyrene-based. Examples of the olefin system include polyethylene, polypropylene, norbornene and the like. Examples of the polyester type include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Examples of the acrylic type include polymethylmethacrylate (PMMA) and the like. Examples of the vinyl type include polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol and the like. Examples of polystyrene-based resins include polystyrene (PS) resin, styrene / acrylonitrile (AS) resin, and styrene / butadiene / acrylonitrile (ABS) resin. Examples of engineering plastic base materials include general-purpose engineering plastics and super engineering plastics. Examples of general-purpose engineering plastics include polycarbonate, polyamide (nylon), and the like. Examples of super engineering plastics include polyetheretherketone (PEEK) and the like. Examples of the thermosetting plastic base material 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 one that has been surface-treated (corona discharge or the like). Further, another layer (for example, an easy-adhesive layer, an anchor layer, etc.) may be provided on one side or both sides of the base material between the layer and the layer formed by the composition of the present disclosure. The base material is preferably polyester-based, and more preferably 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.

As a method of coating the composition of the present disclosure on a substrate, roll coater coating, reverse roll coater coating, bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, etc. Offset printing, flexographic printing, screen printing and the like are exemplified. The amount of coating is not particularly limited, but is usually in the range of 0.01 to 20 g / m ² after drying, preferably 0.025 to 10 g / m ² , and more preferably 0. It is 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, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and none, which emit light in the 150 nm wavelength range or more and 450 nm wavelength range or less. An example is 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. Before irradiation with active energy rays, heating may be performed to dry the cells, if necessary. After irradiation with active energy rays, heating may be performed if necessary to completely cure the cells. The heating conditions are exemplified at about 60 to 150 ° C. for about 30 seconds to 30 minutes, and preferably about 70 to 130 ° C. for about 50 seconds to 10 minutes.

The laminate of the present disclosure may be subjected to a curing treatment, if necessary. The conditions are not particularly limited, but are about 1 to 24 hours at 20 to 50 ° C. By doing so, the solvent resistance of the cured product becomes better.

The cured product of the composition of the present disclosure can exhibit light peeling and solvent resistance. Therefore, a material containing a large amount of organic solvent, such as a cast solution for a resin molded product or an inorganic slurry, can be applied onto the cured product of the composition. The 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 surface to the cured product. Further, the cured product of the composition of the present disclosure includes adhesive tapes, adhesive tapes, double-sided tapes, adhesive labels, protective films (separators) for adhesive surfaces such as seals, resin molded products, synthetic leathers, and decorative boards. It is also useful as a process film used in the manufacture of carbon fiber prepregs, electric / electronic parts, and the like. The cured product of the composition of the present disclosure is a cured product capable of suppressing silicone transferability. Therefore, for applications in which the occurrence of defects due to the transfer of silicone from the cured product is particularly unfavorable, for example, as a process film or process tape for manufacturing electrical / electronic materials (for example, a separator, a carrier film (tape), a transfer film, a protective tape, etc.). Especially useful. In the present disclosure, the electric / electronic material refers to a product group having an electronic circuit, for example, a component constituting a product such as a personal computer, a mobile phone, a liquid crystal display, a refrigerator, and an automobile. That is, the cured product of the present disclosure is useful as a release film and a release film. Further, the cured product of the composition of the present disclosure can suppress the silicone transferability even after the heating step. Therefore, a process film or process tape (for example, separator, carrier film (tape), transfer film, protective tape) for manufacturing electric / electronic materials including heating steps such as drying of solvent, heat curing, and pressure bonding by hot pressing in the manufacturing process. Etc.), which is especially useful.

In addition, it may be used for various purposes such that the effect of the compound (a) of the present disclosure 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. In the examples, parts and% are all 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 Refractometer Detector (RI)
Standard: Monodisperse polystyrene sample: A 20 μL solution obtained by preparing a tetrahydrofuran solution of 0.5 g / mL in terms of solid content and filtering the solution with a microfilter.

<Production Example 1: Synthesis of compound (A-1)>
In a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, one-ended hydroxy-modified silicone (product name "Silaplane FM-0421", manufactured by JNC Co., Ltd., number average molecular weight 5,000), hereinafter "FM-0421". ”) 78.0 parts, 1,1- (bisacryloyloxymethyl) ethyl isocyanate (product name“ Karens BEI ”, manufactured by Showa Denko KK, hereinafter“ BEI ”) 3.7 parts, methquinone 0. After charging 08 parts and 0.03 parts of tin octylate, the temperature was raised until the temperature inside the system reached about 80 ° C., and the temperature was kept for about 1 hour. After confirming the disappearance of the isocyanate peak by IR, the temperature inside the system was lowered to about 50 ° C.
Next, 100 parts of toluene, 0.04 part of diazabicycloundecene (product name "DBU", manufactured by San-Apro Co., Ltd., hereinafter "DBU") and 1-thioglycerol (product name "Blemmer TGL", NOF) After charging 3.4 parts of "TGL" manufactured by Co., Ltd., the temperature was raised until the temperature inside the system reached about 80 ° C., and the temperature was kept for about 2 hours. Then, after confirming that the signal of the acryloyl group disappeared by ^{1 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 charged, and then the temperature was raised until the temperature in the system reached about 80 ° C., and the temperature was kept for about 6 hours. Then, after confirming the disappearance of the peak of isocyanate by IR, the reaction system was cooled to obtain a solution of the compound (A-1) having a solid content of 50% by weight. The number average molecular weight of compound (A-1) was 6,200, and the number of polymerizable unsaturated groups (number of functional groups) was 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 AC1)>
Production Examples 2 to 6, 8, 11 to 12 and Comparative Production Example 1 were carried out by the same method as in Production Example 1 except that the compositions shown in Tables 1 to 3 were changed, and the compounds (A-2) to 1 Solutions of (A-6), (A-8), (A-11) to (A-12) and solutions of (A-C1) were obtained.

<Production Example 7: Synthesis of compound (A-7)>
Production Example 7 was changed to the composition shown in Table 2 and the same method as in Production Example 1 was carried out except that 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)>
In a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 80.4 parts of acryloyl-modified silicone at both ends (product name "X-22-2445", manufactured by JNC Co., Ltd., number average molecular weight 3,200), After charging 100 parts of toluene, 0.08 part of methquinone, 0.04 part of DBU and 5.4 parts of TGL, the temperature was raised to about 80 ° C. and kept warm for about 2 hours. Then, after confirming that the signal of the acryloyl group disappeared by ^{1 1} H-NMR, the temperature in the system was lowered to about 40 ° C.
Next, 14.2 parts of BEI and 0.16 parts of tin octylate were charged, and then the temperature was raised until the temperature in the system reached about 80 ° C., and the temperature was kept for about 6 hours. Then, after confirming the disappearance of the peak of isocyanate by IR, the reaction system was cooled to obtain a solution of the compound (A-9) having a solid content of 50% by weight.

<Production Example 10: Synthesis of compound (A-10)>
In a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 74.5 parts of one-ended dihydroxy-modified silicone (product name "Silaplane FM-DA26", manufactured by JNC Co., Ltd., hereinafter "DA26"), BEI After charging 2.7 parts, 0.08 part of methquinone and 0.03 part of tin octylate, the temperature was raised to about 80 ° C. and kept warm for about 1 hour. After confirming the disappearance of the isocyanate peak by IR, the temperature inside the system was lowered to about 50 ° C.
Next, after charging 100 parts of toluene and 3.6 parts of diethanolamine (product name "diethanolamine (DEA)", manufactured by Mitsui Chemicals, Inc., hereinafter "DEA"), the temperature inside the system rises to about 40 ° C. It was warmed and kept warm for about 2 hours. After confirming that 80% of the acryloyl group was consumed by measuring the amine value, 19.1 parts of BEI and 0.16 parts of tin octylate were charged, and then the temperature in the system reached about 80 ° C. The temperature was raised and kept warm for about 6 hours. Then, after confirming the disappearance of the peak of isocyanate by IR, the reaction system was cooled to obtain a solution of the 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, in a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 96.3 parts of DA26, 3.7 parts of BEI, 0.08 parts of methquinone, and 0.03 parts of tin octylate were used. After charging, the temperature was raised until the temperature inside the system reached about 80 ° C., and the temperature was kept for about 1 hour. After confirming the disappearance of the peak of isocyanate by IR, the reaction system was cooled to obtain a compound (AC2). In Comparative Production Example 3, a compound (A-C3) was obtained by the same method except that the composition was changed to that shown in Table 2.

The meanings of the terms in Tables 1 to 3 are as follows.
FM-0421: One-ended hydroxy-modified silicone (Product name "Silaplane FM-0421", manufactured by JNC Co., Ltd., number average molecular weight 5,000)
FM-3325: Both-terminal amino-modified silicone (product name "Silaplane FM-3325", manufactured by JNC Co., Ltd., number average molecular weight 10,000)
FM-DA26: One-ended dihydroxy-modified silicone (product name "Silaplane FM-DA26", manufactured by JNC Co., Ltd., number average molecular weight 15,0000)
FM-4425: Hydroxy-modified silicone at both ends (product name "Silaplane FM-4425", manufactured by JNC Co., Ltd., 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 KK)
BEI: 1,1- (bisacryloyloxymethyl) ethyl isocyanate (product name "Karenzu BEI", manufactured by Showa Denko KK)
TGL: 1-thioglycerol (product name "Blemmer 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 number of terminal functional groups was confirmed by ¹ H-NMR using the following method.
One-ended dihydroxy-modified silicone (product name "Silaplane FM-DA26", manufactured by JNC Co., Ltd., hereinafter "DA26") and 1,1- (bisacryloyloxymethyl) ethyl isocyanate (product name "Karenzu BEI", Showa Denko) Co., Ltd., hereinafter “BEI”) was mixed at the molar ratio shown in Table 4.
Next, the obtained mixture was measured by ¹ H-NMR, and the integrated value of the signal derived from the acryloyl group (5.8 ppm) was calculated when the integrated value of the signal derived from the methyl group (0 ppm) of polydimethylsiloxane was set to 100. Obtained. Since BEI has two acryloyl groups at the terminal, a straight line showing a proportional relationship was obtained by plotting the number of acryloyl groups and the signal integral value derived from the acryloyl group.
When (A-3) obtained in Production Example 3 is measured by ¹ H-NMR, the integral of the signal derived from the acryloyl group (5.8 ppm) when the signal derived from the methyl group (0 ppm) of polydimethylsiloxane is set to 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 made 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 Toa Synthetic Co., Ltd.), and 4.55 parts of the solution (solid content: 50%) of the compound (A-1) obtained in Production Example 1. A composition (1) containing 23 parts of 1-hydroxycyclohexylphenyl ketone (product name "OMNIRAD 184", manufactured by IGM Resins) as a photopolymerization initiator and diluted with methyl ethyl ketone so that the solid content becomes 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 the compound (A-1) was changed to the solution of the compounds (A-2) to (A-6) and the solution of the compound (A-C1), respectively. The same method as in Example 1 was carried out to obtain compositions (2) to (6) and (C1).

<Example 7: Preparation of composition (7)>
225 parts of dipentaerythritol polyacrylate (product name "NK ester A-9550", manufactured by Shin Nakamura Chemical Industry Co., Ltd.), solution of compound (A-1) obtained in Production Example 1 (solid content: 50%) ) Is 4.6 parts, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (product name "OMNIRAD907", manufactured by IGM RESINS) is 23 parts as a photopolymerization initiator. The composition (7) was prepared by blending and diluting with methyl ethyl ketone so that the solid content was 20%.

<Examples 8 to 9: Preparation of compositions (8) to (9)>
225 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (product name "Viscort # 300", manufactured by Osaka Organic Chemical Industry Co., Ltd.), a solution (solid) of the compound (A-3) obtained in Production Example 3. Minutes: 50%) as 4.55 parts, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (product name "OMNIRAD907", manufactured by IGM RESINS) as a photopolymerization initiator. ) Was blended in 23 parts and diluted with methyl ethyl ketone so as to have a solid content of 20% to prepare the composition (8). In Example 9, the composition (9) was prepared by the same method except that Viscoat # 300 was changed to dipentaerythritol polyacrylate (product name “GM66G0A”, manufactured by Kokusei Kagaku 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 to those shown in the table below, and the compositions (10) to (21) were adjusted.

<Comparative Example 2: Preparation of Composition (C2)>
225 parts of dipentaerythritol polyacrylate (product name "Aronix M403", manufactured by Toa Synthetic Co., Ltd.), 2.27 parts of the solution of the compound (AC2) obtained in Comparative Production Example 2, and photopolymerization started. 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 so as to have a solid content of 20% to prepare a composition (C2).

<Comparative Examples 3 to 4: Preparation of Compositions (C3) to (C4)>
Comparative Example 3 and Comparative Example 4 were carried out by the same method as in Comparative Example 2 except that the solution of the compound (A-C2) was changed to the compound (A-C3) and DA26, respectively, and the composition (C3) and the comparative example 4 were prepared. (C4) was obtained.

<Evaluation example 1: Preparation of laminated body (1)>
The composition (1) is applied to a polyethylene terephthalate film (thickness 75 μm) with a bar coater # 9 (thickness 2 μm after drying), dried at 80 ° C. for 1 minute, and then irradiated with active energy rays (ultraviolet irradiation, irradiance: 520 mw / cm ² , integrated light intensity: 200 mJ / cm ² ), and a laminated body (1) were obtained.

<Evaluation Examples 2 to 21 and Comparative Evaluation Examples 1 to 4: Preparation of laminated bodies (2) to (21) and (C1) to (C4)>
Evaluation Examples 2 to 21 and Comparative Evaluation Examples 1 to 4 were carried out by the same method as in Evaluation Example 1 except that the composition, film thickness and integrated light amount shown in the table were changed, and the laminated bodies (2) to ( 21) and (C1) to (C4) were obtained.

<Performance evaluation (1): Peelability test>
After leaving the laminate overnight, a polyester adhesive tape (product name "No. 31B", manufactured by Nitto Denko Co., Ltd., 20 mm width) was adhered to the surface of the cured product while being pressure-bonded with a 2 kg roller, and the temperature was 23 ° C. It was left for 30 minutes. Next, using a Tensilon universal tester (product name "RTC-1250A", manufactured by A & D Co., Ltd.), the adhesive tape was pulled horizontally at an angle of 180 ° C. (0.3 m / min) and peeled off. The force required for (mN / 20 mm) was measured.

<Performance evaluation (2): Solvent resistance test>
After leaving the laminate overnight, the surface of the cured product was rubbed with a cloth impregnated with MEK 5 times with equal force. Then, a polyester adhesive tape (product name "No. 31B", manufactured by Nitto Denko Corporation, 20 mm width) was adhered to the same place while being pressure-bonded with a 2 kg roller, and left at 23 ° C. for 30 minutes. Next, using a Tensilon universal tester (product name "RTC-1250A", manufactured by A & D Co., Ltd.), the adhesive tape was pulled horizontally at an angle of 180 ° C. (0.3 m / min) and peeled off. The force required for (mN / 20 mm) was measured. At that time, the degree of heavy peeling was evaluated according to the following criteria with respect to the value measured in the 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 Co., Ltd., 20 mm width) was adhered to the surface of the cured product of the laminate left overnight while being pressure-bonded with a 2 kg roller, and then bonded at 23 ° C. for 30 minutes. I left it. Next, the polyester adhesive tape was peeled off, and the Si element content ratio of the surface that was in contact with the cured product coated surface was measured using a scanning X-ray photoelectron spectroscopy analyzer (product name "PHI5000 VersaProbe III", 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 to 7 are as follows.
M403: 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 Industry Co., Ltd.)
# 300: Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (product name "Viscort # 300", manufactured by Osaka Organic Chemical Industry Co., Ltd.)
66G0A: Dipentaerythritol polyacrylate (product name "GM66G0A", manufactured by Kokusei Kagaku Co., Ltd.)
M305: Pentaerythritol tori and tetraacrylate (product name "Aronix M-305", manufactured by Toagosei Co., Ltd.))
184: 1-Hydroxycyclohexylphenyl ketone (product name "OMNIRAD 184", manufactured by IGM Resins)
907: 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (product name "OMNIRAD907", manufactured by IGM RESINS)
MEK: Methyl ethyl ketone IPA: Isopropanol Nv (%) at the time of coating: Concentration of active ingredient at the time of coating

Claims (7)

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).
The compound (a) according to the general formula (1), which is a reaction product of a component containing.
General formula (1):

(In general formula (1),
X ₁ to X ₂ and X ₅ to X ₆ are independently alkyl groups having 1 or more and 4 or less carbon atoms.
Each of X3 to _X4 is an alkyl group having 1 or more carbon atoms and ₄ or less carbon atoms, and may be the same or different for each repeating unit.
n is an integer of 1 or more and 400 or less.
Y ₁ and Y ₂ are independent of each other.
(I) A structure (I-II) containing a hydrocarbon group (I-I) having 1 or more and 20 or less carbon atoms which may have an ether bond, a bond A and a bond B, and a polymerizable unsaturated group (I-). A structure containing III) in this order, or a structure containing (II) a hydrocarbon group (II-I) having 1 or more and 20 or less carbon atoms which may have an ether bond, a bond A or a bond B (II-). It is a structure containing one or more selected from the group consisting of II) and a polymerizable unsaturated group (II-III).
At least one of Y ₁ and Y ₂ is (I),
The total number of polymerizable unsaturated groups of Y ₁ and Y ₂ is 4 or more.
Bond A is one or more bonds selected from the structural formulas (1) to (3).
Structural formula (1)

And
Structural formula (2)

And
Structural formula (3)

And
Bond B is a urethane bond. ) (A-3) The compound (a) according to claim 1, wherein the number of isocyanate groups in the component is one. (A-2) The component 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. One or more of the following or from diethanolamine, 2-piperidinethanol, 2-piperidinethanol, 3-piperidinmethanol, 3-piperidinethanol, 4-piperidinmethanol, 4-piperidinethanol, 2-piperidinol, 3-piperidinol and 4-piperidinol. One or more species selected from the group of
(A-3) A group consisting of 2- (meth) acryloyloxyethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate and 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate. The compound (a) according to claim 1 or 2, which is one or more selected from the above. The compound (a) according to any one of claims 1 to 3.
A component (b) containing two or more (meth) acryloyl groups, and a photopolymerization initiator (c).
An active energy ray-curable coating agent composition containing. A release coating agent composition comprising the active energy ray-curable coating agent composition according to claim 4. A laminate containing a substrate and a cured product of the active energy ray-curable coating agent composition according to claim 4 or a cured product of the release coating agent composition according to claim 5. Lamination including a step of curing the active energy ray-curable coating agent composition according to claim 4 or the release coating agent composition according to claim 5 coated on at least one surface of a substrate with active energy rays. How to make a body.