JP2018021186A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition used for obtaining a cured product excellent in mold releasability, adhesion to a resin substrate, low warpage, and toughness.SOLUTION: The curable resin composition is used which contains: an ethylenically unsaturated monomer (A) having a urethane group; a monofunctional ethylenically unsaturated monomer (B) having no urethane group; a polyfunctional ethylenically unsaturated monomer (C) having no urethane group; a silane compound (D) represented by a specific chemical structural formula; and a radical polymerization initiator (E).SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition.

  Conventionally, prism lenses used in liquid crystal displays and optical lenses such as Fresnel lenses and lenticular lenses used in projection TVs are made by pouring a curable resin composition into a mold in which a resin base material is set on the inner surface of the mold. It is manufactured by irradiating with active energy rays and curing.

  Since these prism sheets and optical lenses have fine and fine irregularities on their surfaces, they are easily scratched, and a method for introducing a rigid chemical structure such as a bisphenol skeleton is known as a prevention method. (For example, refer to Patent Document 1).

However, the method of introducing a rigid chemical structure such as a bisphenol skeleton in order to prevent damage to the uneven shape has a problem that mold releasability is poor.
Also, in general, mold releasability and adhesion to a resin base material are contradictory properties, and there is a known problem that adhesion to a resin base material is lowered when trying to improve mold releasability. It has been.

  By the way, generally, the curable resin composition is required to have low warpage, and when the crosslinking density of the curable resin composition is lowered, a curable resin composition having low warpage can be obtained. As a method of reducing the crosslinking density, it is known to reduce the content ratio of the polyfunctional ethylenically unsaturated monomer to increase the content ratio of the monofunctional ethylenically unsaturated monomer. When the content ratio of the monomer is reduced too much, the toughness is deteriorated.

  Generally, as a method for improving toughness, a method for increasing the content ratio of a polyfunctional ethylenically unsaturated monomer, a method for introducing a rigid chemical structure, and a method for introducing a chemical structure that causes an interaction such as hydrogen bonding are introduced. Etc. are known. However, if the content ratio of the polyfunctional ethylenically unsaturated monomer is increased too much, the warping property increases, and the rate of introduction of a rigid chemical structure and / or the rate of introduction of a chemical structure that causes an interaction such as hydrogen bonding is increased. If it is too much, the cured film becomes brittle, resulting in a decrease in toughness.

  In the field of optical components such as prism sheets and optical lenses, the mold releasability of cured products, adhesion to resin base materials, low warpage and toughness are all important performances, but all these are sufficient. A curable resin composition having a high performance has not yet been found.

JP-A-11-240926

  The objective of this invention is providing the curable resin composition used in order to obtain the hardened | cured material which is excellent in mold release property, the adhesiveness to a resin base material, low curvature property, and toughness.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention relates to an ethylenically unsaturated monomer having a urethane group (A), a monofunctional ethylenically unsaturated monomer having no urethane group (B), and a polyfunctional ethylenically unsaturated monomer having no urethane group. A curable resin composition comprising a monomer (C), a silane compound (D) represented by the following general formula (1), and a radical polymerization initiator (E); the curable resin composition Is a cured product.

[In General Formula (1), R ¹ O represents an alkoxy group having 1 to 4 carbon atoms; X represents an alkyl group, a (meth) acryloyloxyalkyl group, an aminoalkyl group, a vinyl group, or a glycidoxyalkyl. Group, vinylphenyl group, isocyanate alkyl group, isocyanurate group, ureidoalkyl group or mercaptoalkyl group; when there are plural groups, R ¹ O and X may be the same or different; n is an integer of 1 to 3 It is. ]

  The cured product obtained by curing the curable resin composition of the present invention has the effect of being excellent in mold releasability, adhesion to a resin substrate, low warpage, and toughness.

  The curable resin composition of the present invention includes an ethylenically unsaturated monomer having a urethane group (A), a monofunctional ethylenically unsaturated monomer having no urethane group (B), and a polyfunctional having no urethane group. It contains an ethylenically unsaturated monomer (C), a silane compound (D) represented by the above general formula (1), and a radical polymerization initiator (E).

  The ethylenically unsaturated monomer (A) having a urethane group as the first essential component of the curable resin composition of the present invention is a monomer having at least one ethylenically unsaturated group and a urethane group. .

By containing the ethylenically unsaturated monomer (A) in the curable resin composition, toughness can be imparted to the cured product, and the toughness and elongation of the cured product can be adjusted.
Here, examples of the ethylenically unsaturated group include a (meth) acryloyl group, a vinyl group, an allyl group, and a propenyl group.
In the present invention, the expression “(meth) acryloyl” means acryloyl and / or methacryloyl, the expression “(meth) acrylate” means acrylate and / or methacrylate, and “(meth) acrylic”. "" Means acrylic and / or methacrylic, "(meth) acryloyloxy" means acryloyloxy and / or methacryloyloxy, "(meth) allyl" means allyl and / or Means methallyl.

  The ethylenically unsaturated monomer (A) having a urethane group can be obtained by reacting an organic diisocyanate (a), a diol (b), and a (meth) acrylate (c) having a hydroxyl group.

Examples of the organic diisocyanate (a) include an aromatic ring-containing diisocyanate (a1), an alicyclic diisocyanate (a2), and a chain aliphatic diisocyanate (a3).
(A) may be used individually by 1 type, or may use 2 or more types together.

  Examples of the diisocyanate (a1) having an aromatic ring include 1,3- or 1,4-phenylene diisocyanate 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4′- or 2,4′-diphenylmethane. Diisocyanate (MDI), m- or p-isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl- 4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate and m- or p-isocyanatophenylsulfonyl isocyanate, m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α ′ -Tetramethylxylylene diisocyanate (TMXDI) etc. are mentioned.

  Examples of the alicyclic diisocyanate (a2) include isophorone diisocyanate (IPDI), 2,4- or 2,6-methylcyclohexane diisocyanate (hydrogenated TDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexyl. Examples thereof include silylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, and dimer acid diisocyanate.

  As the chain aliphatic diisocyanate (a3), ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4 -Or 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) fumarate, bis ( 2-isocyanatoethyl) carbonate and trimethylhexamethylene diisocyanate (TMDI).

Preferred as the organic diisocyanate (a) in the present invention is a diisocyanate (a1) having an aromatic ring, and more preferred are XDI, TMXDI, MDI and TDI.
By using these diisocyanates as the organic diisocyanate (a), the crystallinity of the ethylenically unsaturated monomer (A) having a urethane group is improved, and as a result, the cured product of the curable resin composition is separated. Improved moldability and excellent toughness.

As the diol (b), a diol (b1) having an aromatic ring, an alicyclic diol (b2), a chain aliphatic diol (b3), and alkylene oxide thereof [ethylene oxide (hereinafter sometimes abbreviated as EO)]. 1,2- or 1,3-propylene oxide (hereinafter sometimes abbreviated as PO) and 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, etc.] adducts, etc. Can be mentioned.
(B) may be used individually by 1 type, or may use 2 or more types together.

  Examples of the diol (b1) having an aromatic ring include resorcinol, hydroquinone, naphthalenediol, bisphenol A, bisphenol F, and bisphenol S.

  As the alicyclic diol (b2), 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 1, Examples include 4-bis (hydroxymethyl) cyclohexane and 2,2-bis (4-hydroxycyclohexyl) propane.

  As the chain aliphatic diol (b3), a linear aliphatic diol [ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 7-heptanediol, 1,8-octanediol, 1,9-nonanediol and 1,10-dodecanediol] and branched aliphatic diols [1,2-, 1,3- or 2,3-butane Diol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-methyl-1,5-pentanediol and 3-methyl-1,5-pentane Diol etc.].

The diol (b) in the present invention is preferably a diol (b1) having an aromatic ring.
By using the diol (b1) as the diol (b), the crystallinity of the cured product is improved and the mold releasability is improved.
Among the diols (b1), the diol (b1) having an aromatic ring and addition of alkylene oxide thereof are preferable from the viewpoint of the reactivity of the urethanization reaction and the coloration of the cured product cured by irradiation with active energy rays. From the viewpoint of improving the crystallinity of a cured product cured by irradiation with active energy rays, a 1-10 mol alkylene oxide adduct of bisphenol A is more preferable, and propylene of bisphenol A is particularly preferable. Examples thereof include an oxide 2 mol adduct and a bisphenol A ethylene oxide 10 mol adduct.

Examples of the (meth) acrylate (c) having a hydroxyl group include hydroxyalkyl (meth) acrylate (c1), polyalkylene glycol mono (meth) acrylate (c2), and alkylol (meth) acrylamide (c3).
(C) may be used individually by 1 type, or may use 2 or more types together.

  Examples of the hydroxyalkyl (meth) acrylate (c1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate.

  Examples of the polyalkylene glycol mono (meth) acrylate (c2) include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate.

  Examples of alkylol (meth) acrylamide (c3) include N-methylol (meth) acrylamide.

  Among these, hydroxyalkyl (meth) acrylate (c1) is preferable from the viewpoint of urethanization reactivity and mold releasability of the cured product, and hydroxyethyl (meth) acrylate is more preferable.

As the ethylenically unsaturated monomer (A) having a urethane group in the present invention, from the viewpoint of toughness of the cured product, diisocyanate (a1) having an aromatic ring, diol (b1) having an aromatic ring [(b1) An alkylene oxide adduct is also included] and a product obtained by reacting at least one of (meth) acrylate (c) having a hydroxyl group is preferable.
Moreover, (A) may be used individually by 1 type, or may use 2 or more types together.

  Isocyanate group / hydroxyl group equivalent ratio in the reaction of organic diisocyanate (a) with diol (b) and hydroxyl group-containing (meth) acrylate (c) [isocyanate group of (a) / hydroxyl group of (b) and (c ) Is not particularly limited, but is preferably 1 / 0.5 to 1/10, more preferably 1 / 0.7 to 1/5, and particularly preferably 1 / 0.5 from the viewpoint of storage stability. 1 to 1/2.

The number average molecular weight (hereinafter sometimes abbreviated as Mn) of the ethylenically unsaturated monomer (A) having a urethane group is preferably 500 to 50,000, more preferably 700 to 20, 000.
When Mn is 500 or more, the toughness of the cured product is excellent, and when it is 50,000 or less, the mold shape reproducibility of the cured product is excellent.

In addition, Mn in this invention can be measured on condition of the following by the gel permeation chromatography (GPC) method.
[1] Apparatus: Gel permeation chromatography “HLC-8120GPC”, manufactured by Tosoh Corp. [2] Column: “TSKgel GMHXL” x 2 + “TSKgel Multipore HXL-M”, manufactured by Tosoh Corp. [3] Eluent: Tetrahydrofuran [4] Reference material: Standard polystyrene (TSK standard POLYSTYRENE), manufactured by Tosoh Corporation [5] Injection conditions: Sample concentration 0.25 wt%, column temperature 40 ° C.

The ethylenically unsaturated monomer (A) having a urethane group in the present invention is produced by reacting an organic diisocyanate (a), a diol (b) and a (meth) acrylate (c) having a hydroxyl group by a known method. be able to.
Especially, it is preferable to manufacture by making the urethane prepolymer (d) which has an isocyanate group obtained by making (a) and (b) react, and (c).
In the reaction between (a) and (b) and the reaction between (d) and (c), a urethanization catalyst may be used.
Examples of the urethanization catalyst include metal compounds (such as organic bismuth compounds, organic tin compounds, and organic titanium compounds) and quaternary ammonium salts.

The monofunctional ethylenically unsaturated monomer (B) having no urethane group, which is the second essential component of the curable resin composition of the present invention, has no urethane group and only one ethylenically unsaturated group. If it is a polymerizable monomer which has, it will not be specifically limited. Preferably it is a monomer which does not have a urethane group and contains one (meth) acryloyl group as an ethylenically unsaturated group.
However, as the ethylenically unsaturated monomer (B), a silane compound (D1) having a (meth) acryloyloxyalkyl group described later and an ethylenically unsaturated monomer (F) having a functional group (a) except for.

Monofunctional ethylenically unsaturated monomer (B) having no urethane group includes mono (meth) acrylate (B1) having an alicyclic hydrocarbon group, mono (meth) acrylate (B2) having an aromatic ring, hydroxyl group And mono (meth) acrylate (B3), mono (meth) acrylamide derivative (B4), and other monofunctional ethylenically unsaturated monomers.
In addition, (B) may be used individually by 1 type, or may use 2 or more types together.

  As mono (meth) acrylate (B1) having an alicyclic hydrocarbon group, cyclohexyl (meth) acrylate, 4-t-butyl-cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) Examples include acrylate and adamantyl (meth) acrylate.

  As mono (meth) acrylate (B2) having an aromatic ring, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, o-, m- or p-phenylphenol mono (meth) acrylate, 3,3′- Examples include mono (meth) acrylate of diphenyl-4,4′-dihydroxybiphenyl and nonylphenoxypolyethylene glycol (meth) acrylate.

  As mono (meth) acrylate (B3) having a hydroxyl group, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meta) ) Acrylates and mono (meth) acrylates of polyethylene glycol-polypropylene glycol block polymers.

  Mono (meth) acrylamide derivatives (B4) include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N , N′-dimethyl (meth) acrylamide, N, N′-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide and (meta ) Acryloylmorpholine and the like.

  Examples of other monofunctional ethylenically unsaturated monomers include (meth) acrylic acid, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate.

The polyfunctional ethylenically unsaturated monomer (C) having no urethane group as the third essential component of the curable resin composition of the present invention is a polymerizable monomer containing two or more ethylenically unsaturated groups. There is no particular limitation as long as it is a monomer. A polymerizable monomer having 2 to 6 (meth) acryloyl groups is preferable.
However, (C) excludes a silane compound (D1) having a (meth) acryloyloxyalkyl group described later and an ethylenically unsaturated monomer (F) having a functional group (a).

The polymerizable monomer having 2 to 6 (meth) acryloyl groups is, for example, 2 to 2 having no urethane group in the molecule among (meth) acrylates obtained by reacting polyol and (meth) acrylic acid. It is a hexafunctional (meth) acrylate.
Specific examples include (C1) to (C5) below.

Examples of 2 to 6 functional (meth) acrylate (C) having no urethane group include di (meth) acrylate (C1), tri (meth) acrylate (C2), tetra (meth) acrylate (C3), and penta (meth) ) Acrylate (C4) and hexa (meth) acrylate (C5).
In addition, (C) may be used individually by 1 type, or may use 2 or more types together.

  Examples of the di (meth) acrylate (C1) include bifunctional polyoxyalkylene polyol (meth) acrylate (C11) and other bifunctional (meth) acrylate (C12).

  As the bifunctional polyoxyalkylene polyol (meth) acrylate (C11), the number of (meth) acryloyl groups in the molecule is 2, and the compound (C1) having 2 to 30 oxyalkylene groups in the molecule Is preferred. The oxyalkylene group preferably has 2 to 4 carbon atoms.

Specific examples include (C11) below.
Di (meth) acrylate of alkylene oxide adduct to chain aliphatic polyhydric alcohol [di (meth) acrylate of ethylene oxide adduct of trimethylolpropane, di (meth) acrylate of ethylene oxide adduct of glycerin, polyoxy Ethylene glycol di (meth) acrylate, polyoxypropylene glycol di (meth) acrylate [tripropylene glycol di (meth) acrylate, etc.] and polyoxytetramethylene glycol di (meth) acrylate];
Di (meth) acrylate [EO-modified hydrogenated bisphenol A diacrylate and the like] of an alkylene oxide adduct to an alicyclic polyhydric alcohol;
Di (meth) acrylate of an alkylene oxide adduct to a polyhydric alcohol having an aromatic ring [compound represented by the following general formula (2): di (meth) acrylate of EO4 mol adduct to bisphenol A, bisphenol A Di (meth) acrylate etc. of EO 20 mol adduct to] and the like.

In general formula (2), each R ² is independently a hydrogen atom or a methyl group. For example, when two R ² are methyl groups, they are bisphenol A skeletons, and when two R ² are hydrogen atoms, they are bisphenol Fs. It is a skeleton.

In general formula (2), each R ³ is independently a hydrogen atom or a methyl group. When R ³ is a hydrogen atom, it corresponds to addition of ethylene oxide, and when it is a methyl group, it corresponds to addition of propylene oxide. The addition form of these alkylene oxides may be ethylene oxide single addition or propylene oxide single addition, or in the case of combined use of ethylene oxide and propylene oxide, block addition or random addition.
m and k are each independently a number of 1 to 30, represent the added mole number of ethylene oxide and / or propylene oxide, and (m + k) is 2 to 60. Preferably, the number of m and k is 2 to 20 and (m + k) is 4 to 40.

In general formula (2), each R ⁴ is independently a hydrogen atom or a methyl group. When R ⁴ is a hydrogen atom, the acryloyl group is terminal, and when R ⁴ is a methyl group, the methacryloyl group is terminal. Preferably it is a hydrogen atom.

As other bifunctional (meth) acrylate (C12), di (meth) acrylate of chain aliphatic polyhydric alcohol [compound having 9 to 25 carbon atoms: di (meth) acrylate of glycerin, di (meth) acrylate of trimethylolpropane ( (Meth) acrylate, di (meth) acrylate of 3-hydroxy-1,5-pentanediol, di (meth) acrylate of 2-hydroxy-2-ethyl-1,3-propanediol, 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate and 2-n-butyl-2-ethyl -1,3-propanediol di (meth) acrylate and the like];
Di (meth) acrylate of polyhydric alcohol having alicyclic skeleton [compound having 10 to 30 carbon atoms: dimethylol tricyclodecane di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate and dicyclopentane dimethylol di (Meth) acrylate etc.];
Di (meth) acrylate of a polyhydric alcohol having an aromatic ring [trimethylolpropane benzoate di (meth) acrylate];
Hydroxyl group-containing both-end epoxy acrylate; and esterified products of polyhydric alcohol, (meth) acrylic acid and hydroxycarboxylic acid [for example, hydroxypivalic acid neopentyl glycol di (meth) acrylate] and the like.

  Examples of tri (meth) acrylate (C2) include ethoxylated trimethylolpropane triacrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol tri (meth) acrylate.

  Examples of tetra (meth) acrylate (C3) include ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate.

  Examples of penta (meth) acrylate (C4) include dipentaerythritol penta (meth) acrylate.

  Examples of hexa (meth) acrylate (C5) include dipentaerythritol hexa (meth) acrylate.

  Among (C), from the viewpoint of toughness, di (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol, which are EO addition products of bisphenol A, are preferable. Penta (meth) acrylate and pentaerythritol tetra (meth) acrylate.

  The fourth essential component silane compound (D) of the curable resin composition of the present invention is represented by the general formula (1).

In the general formula (1), R ¹ O represents an alkoxy group having 1 to 4 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, etc.). Further, when there are a plurality of R ¹ Os, they may be the same or different.
N is an integer of 1 to 3.

In the general formula (1), X represents an alkyl group, a (meth) acryloyloxyalkyl group, an aminoalkyl group, a vinyl group, a glycidoxyalkyl group, a vinylphenyl group, an isocyanate alkyl group, an isocyanurate group, a ureidoalkyl group, or Mercaptoalkyl group. Further, when there are a plurality of Xs, they may be the same or different.
Of these, a (meth) acryloyloxyalkyl group or an aminoalkyl group is preferable.
As for these silane compounds (D), for example, chemical product names and structural formulas are illustrated for each functional group in a list of product brochures of silane coupling agents of Shin-Etsu Silicone Co., Ltd.

Examples of the silane compound (D) represented by the general formula (1) include (meth) acryloyloxyalkyltrialkoxysilane, aminoalkyltrialkoxysilane, di (meth) acryloyloxydialkoxysilane, and diaminoalkyldialkoxysilane. , Tri (meth) acryloyloxyalkylalkoxysilane, and triaminoalkylalkoxysilane.
In addition, (D) may be used individually by 1 type, or may use 2 or more types together.

In the general formula (1), as the silane compound (D1) having a (meth) acryloyloxyalkyl group as X, (meth) acryloyloxyalkyltrialkoxysilane, bis [(meth) acryloyloxyalkyl] dialkoxy Examples include silane and tris [(meth) acryloyloxyalkyl] alkoxysilane.
Specific examples include the following compounds.
Examples of the silane compound in which n is 3, that is, three alkoxy groups include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and the like.

  Examples of the silane compound in which n is 2, that is, two alkoxy groups include bis [3- (meth) acryloyloxypropyl] dimethoxysilane, bis [3- (meth) acryloyloxypropyl] diethoxysilane, and the like. .

  Examples of the silane compound in which n is 1, that is, one alkoxy group, include tris [3- (meth) acryloyloxypropyl] methoxysilane, tris [3- (meth) acryloyloxypropyl] ethoxysilane, and the like.

In the general formula (1), examples of the silane compound (D2) having an aminoalkyl group as X include aminoalkyltrialkoxysilane, bis (aminoalkyl) dialkoxysilane, and tris (aminoalkyl) alkoxysilane.
Specific examples include the following compounds.
Examples of silane compounds having n of 3, that is, 3 alkoxy groups include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, Examples include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

  Examples of silane compounds in which n is 2, that is, two alkoxy groups include bis [N- (2-aminoethyl) -3-aminopropyl] dimethoxysilane and bis [N- (2-aminoethyl) -3-aminopropyl. ] Diethoxysilane, bis (3-aminopropyl) dimethoxysilane, bis (3-aminopropyl) diethoxysilane and the like.

  Examples of the silane compound in which n is 1, that is, one alkoxy group include tris [N- (2-aminoethyl) -3-aminopropyl] methoxysilane, tris [N- (2-aminoethyl) -3-aminopropyl. And ethoxysilane, tris (3-aminopropyl) methoxysilane, tris (3-aminopropyl) ethoxysilane, and the like.

In the general formula (1), examples of the silane compound (D3) having a glycidoxyalkyl group as X include the following compounds.
Examples of the silane compound in which n is 3, that is, three alkoxy groups include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane.

  Examples of the silane compound in which n is 2, that is, two alkoxy groups include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like.

  Examples of the silane compound in which n is 1, that is, one alkoxy group, include 3-glycidoxypropyldimethylmethoxysilane and 3-glycidoxypropyldimethylethoxysilane.

In the general formula (1), examples of the silane compound (D4) having a mercaptoalkyl group as X include the following compounds.
Examples of the silane compound in which n is 3, that is, three alkoxy groups include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like.

  Examples of the silane compound in which n is 2, that is, two alkoxy groups include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethoxysilane.

  Examples of the silane compound in which n is 1, that is, one alkoxy group, include 3-mercaptopropyldimethylmethoxysilane and 3-mercaptopropyldimethylethoxysilane.

Among the silane compounds (D) represented by the general formula (1), the silane compound (X) in the general formula (1) in which X is a (meth) acryloyloxyalkyl group is preferable from the viewpoint of substrate adhesion. In D1) and general formula (1), X is a silane compound (D2) having an aminoalkyl group.
Further preferred are a silane compound having three alkoxy groups and one (meth) acryloyloxyalkyl group, and a silane compound having three alkoxy groups and one aminoalkyl group. Particularly preferred are 3- (meth) acryloyloxypropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, most preferred is 3- (meth) acryloyloxypropyl. Trimethoxysilane.

Examples of the radical polymerization initiator (E) as the fifth essential component of the curable resin composition of the present invention include a photopolymerization initiator (E1) and a thermal polymerization initiator (E2).
As a photoinitiator (E1), a benzoin compound (E1-1), an alkylphenone compound (E1-2), an anthraquinone compound (E1-3), a thioxanthone compound (E1-4), a ketal compound (E1-5) Benzophenone compound (E1-6), phosphine oxide compound (E1-7), oxime ester compound (E1-8) and the like.
(E) may be used individually by 1 type, or may use 2 or more types together.

  Examples of the benzoin compound (E1-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether.

  Examples of the alkylphenone compound (E1-2) include acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl- Phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2- (dimethylamino)- 2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like can be mentioned.

  Examples of the anthraquinone compound (E1-3) include 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone.

  Examples of the thioxanthone compound (E1-4) include 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone.

  Examples of the ketal compound (E1-5) include acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Examples of the benzophenone compound (E1-6) include benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone, and the like.

  Examples of the phosphine oxide (E1-7) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide and bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.

  Examples of the oxime ester compound (E1-8) include 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime) and ethanone-1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Examples of the thermal polymerization initiator (E2) include an organic peroxide (E2-1) and an azo initiator (E2-2).

  As the organic peroxide (E2-1), 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane 2,2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, dilauroyl peroxide, t-hexylperoxyisopropyl monocarbonate, t -Butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy Laurate, t-butylperoxypivalate, t-hexylperoxypivalate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t- Butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, 2,2-bis (t-butyl Peroxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butyl) Peroxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2, -Di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexin-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide and t-butyl hydroperoxide Examples include oxides.

  As the azo initiator (E2-2), 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4- Examples thereof include dimethylvaleronitrile, azodi-t-octane and azodi-t-butane.

  The organic peroxide (E2-1) contains a reducing agent [bisulfite (sodium bisulfite, potassium bisulfite, ammonium bisulfite, etc.), reducing metal salt [iron (II) sulfate, etc.], transition metal salt. Amine complexes [pentamethylenehexamine complex of cobalt (III) chloride and diethylenetriamine complex of copper (II) chloride] and organic reducing agents [ascorbic acid, tertiary amine (dimethylaminobenzoic acid (salt), dimethylaminoethanol, etc.) ) Etc.] etc.] can also be used to cure the curable resin composition using a redox reaction.

  When the thermal polymerization initiator is used alone, it may be carried out in accordance with conventional means of radical thermal polymerization. In some cases, it is used in combination with the photopolymerization initiator (E1), and for the purpose of further improving the reaction rate after photocuring. Thermosetting can also be performed.

Among these radical polymerization initiators (E), the photopolymerization initiator (E1) is preferable from the viewpoint of shortening the process time for curing the curable resin composition.
Of the photopolymerization initiator (E1), the alkylphenone compound (E1-2) and the phosphine oxide (E1-7) are preferable from the viewpoint of light resistance that the cured product is hardly yellowed, and more preferable. 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis- (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, particularly preferred are 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

In the curable resin composition of the present invention, at least one functional group selected from the group consisting of a carboxy group, a phosphate group, a phosphate ester group, and a sulfo group (for the purpose of improving the adhesion to a substrate) You may further contain the ethylenically unsaturated monomer (F) which has a).
In addition, the said ethylenically unsaturated monomer which has the said functional group (a) and a urethane group is handled as the said ethylenically unsaturated monomer (A) which has a urethane group.

Examples of the ethylenically unsaturated monomer (F) include a vinyl monomer having a carboxy group, a vinyl monomer having a phosphate group, a vinyl monomer having a phosphate ester group, and a vinyl monomer having a sulfo group.
In addition, (F) may be used individually by 1 type, or may use 2 or more types together.

  Examples of vinyl monomers having a carboxy group include unsaturated monocarboxylic acids, unsaturated polyvalent (2-4 valent) carboxylic acids, unsaturated polyvalent carboxylic acid alkyl esters, and salts thereof [alkali metal salts (sodium salts and potassium salts). Etc.), alkaline earth metal salts (calcium salts and magnesium salts, etc.), amine salts and ammonium salts, etc.].

  Examples of the vinyl monomer having a carboxy group include 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and 2-acryloyloxyethyl-phthalic acid.

  Examples of the vinyl monomer having a phosphoric acid group include 2- (meth) acryloyloxyethyl acid phosphate and caprolactone-modified [2-{(meth) acryloyloxy} ethyl] acid phosphate.

  Examples of the vinyl monomer having a phosphate ester group include a phosphate ester compound containing a (meth) acryloyl group, and specifically, bis [2-{(meth) acryloyloxy} ethyl] acid phosphate, caprolactone. Modified bis [2-{(meth) acryloyloxy} ethyl] acid phosphate, caprolactone modified bis [2-{(meth) acryloyloxy} methyl] acid phosphate, caprolactone modified bis [2-{(meth) acryloyloxy} propyl] acid Examples include phosphate, caprolactone-modified bis [2-{(meth) acryloxy} butyl] acid phosphate, and the like.

  Examples of the vinyl monomer having a sulfo group include vinyl sulfonic acid, (meth) allyl sulfonic acid, 2- (meth) acryloylamido-2-methylpropane sulfonic acid, and salts thereof.

Among these ethylenically unsaturated monomers (F), a vinyl monomer having a phosphate group and a vinyl monomer having a phosphate ester group are preferable from the viewpoint of adhesion of the cured product, and caprolactone is more preferable. Modified [2-{(meth) acryloyloxy} ethyl] acid phosphate.
Such an ethylenically unsaturated monomer (F) can be obtained from the market as KAYAMER PM-21 [manufactured by Nippon Kayaku Co., Ltd.].

  The curable resin composition of the present invention may further contain an organic acid ester compound (G) for the purpose of improving the adhesion to the substrate.

Examples of the organic acid ester compound (G) include phosphoric acid ester (G1), carboxylic acid ester (G2), and sulfonic acid ester (G3).
Specifically, inorganic phosphoric acid (such as phosphoric acid, phosphoric anhydride, phosphorus oxide and polyphosphoric acid), alkyl carboxylic acid (such as phthalic acid) or alkyl sulfonic acid (linear alkyl benzene sulfonic acid and branched alkyl benzene sulfonic acid); Alcohol having 1 to 24 carbon atoms (methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, dodecanol, tridecanol, tetradecane And alkylene oxide adducts of alcohols having 1 to 24 carbon atoms (EO 2 mol adduct of dodecanol, 10 mol adduct of tridecanol EO, PO 2 mol adduct of tetradecanol, stearyl) Ester compounds such as alcohol EO10 mole adduct], and the like.
However, as the organic acid ester compound (G), an ethylenically unsaturated monomer (F) having at least one functional group (a) selected from the group consisting of the carboxy group, the phosphoric acid group and the sulfo group. )except for.

  The organic acid ester compound (G) is preferably a phosphate ester (G1), more preferably a reaction product of an alcohol having 1 to 24 carbon atoms and inorganic phosphoric acid, and inorganic phosphoric acid and carbon. Dibutyl phosphate is particularly preferred as a reaction product of an alkylene oxide adduct of an alcohol having a number of 1 to 24.

The curable resin composition of the present invention may further contain a salt (H) of a phosphate ester and an amine for the purpose of improving mold releasability.
Examples of the salt (H) of phosphoric acid ester and amine include a reaction product of phosphoric acid ester and amine (a mixture of salts generated upon reaction).

Examples of the phosphate ester as a raw material include a reaction product of an alcohol having 6 to 24 carbon atoms and inorganic phosphoric acid, a reaction product of an alkylene oxide adduct of an alcohol having 6 to 24 carbon atoms and inorganic phosphoric acid, and the like.
Examples of inorganic phosphoric acid include phosphoric acid, phosphoric anhydride, phosphorus oxide, and polyphosphoric acid.
Preferred as the phosphate ester is a reaction product of tridecanol and inorganic phosphoric acid.
Examples of the alcohol having 6 to 24 carbon atoms include those having 6 or more carbon atoms among the alcohols having 1 to 24 carbon atoms.

Examples of the raw material amine include tertiary aliphatic amines, secondary aliphatic amines, primary aliphatic amines, and alkylene oxide adducts thereof.
In addition, carbon number of alkylene oxide here is 2-4, and may be individual or may use 2 or more types together.

  Of the raw material amines, from the viewpoint of mold releasability of the cured product, a tertiary aliphatic amine is preferable, and N, N-dimethylstearylamine is more preferable.

Of the salt (H) of phosphate ester and amine, from the viewpoint of imparting mold releasability and adhesion to the substrate, inorganic phosphate reaction products of alcohols having 6 to 24 carbon atoms and tertiary aliphatics are preferred. A salt comprising an amine is preferable, and a salt of 2-ethylhexyl alcohol with an inorganic phosphoric acid reactant and N, N-dimethylstearylamine, and an inorganic phosphoric acid reactant of a tridecanol EO adduct with N, N- It is a salt with dimethylstearylamine.
The equivalent ratio of phosphate ester to amine is preferably 1.1 / 1.0 to 1.0 / 1.0.

If necessary, the curable resin composition of the present invention may contain other additives (I) as long as the effects of the present invention are not impaired.
Other additives (I) include a colorant (I1), an antioxidant (I2), an ultraviolet absorber (I3), a polymerization inhibitor (I4), a chain transfer agent (I5), a filler (I6), Surfactant (I7), plasticizer (I8), organic solvent (I9), thixotropy imparting agent (thickener) (I10), and the like can be mentioned, and various types can be selected according to the purpose. Either single use or a combination of two or more may be used.

  The curable resin composition of the present invention preferably contains an antioxidant (I2) and an ultraviolet absorber (I3) as necessary from the viewpoint of suppressing the cured product from being deteriorated by light.

  As the antioxidant (I2), 2,6-di-t-butyl-4-methylphenol, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4 -Methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 6- [3- (3-t -Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,6,10-tetra-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3-4'-hydroxy -3′-5′-di-t-butylphenyl) propionic acid-n-octadecyl, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, 3,9-bis [ 2- [3- 3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] undecane, 2,2′-methylenebis (6-tert-butyl-4-methylphenol), 4,4′butylidenebis (6-tert-butyl-3-methylphenol), 3,6-dioxaoctamethylene = bis [3- (3-tert-butyl) -4-hydroxy-5-methylphenyl) propionate], 4,4'-thiobis (2-tert-butyl-5-methylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol) Thiodiethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′- Droxybenzyl) isocyanuric acid, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, pentaerythrityl tetrakis [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate] and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene.

  Examples of the ultraviolet absorber (I3) include benzotriazole [2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole and 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole etc.], triazine [2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol etc.], benzophenone (2-hydroxy-4-n-octyloxybenzophenone etc.) and Shu Acid anilide (2-ethoxy-2'-ethyl oxalic acid bisanilide etc.) etc. are mentioned.

  In the method for producing a cured product using active energy rays of the curable resin composition of the present invention, the molding temperature is about 50 to 90 ° C. in many cases, depending on the active energy ray generator. From the viewpoint of avoiding polymerization and improving the stability of the monomer, it is preferable to add a polymerization inhibitor (I4). Moreover, it is preferable to contain a polymerization inhibitor (I4) also from the point of the storage stability of curable resin composition.

As the polymerization inhibitor (I4), phenol compounds [hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis- (4-methyl-6-t-butylphenol) ) And 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane], sulfur compounds (dilauryl thiodipropionate, etc.), phosphorus compounds (triphenyl phosphite, etc.) ) And amine compounds (such as phenothiazine).
The weight ratio of the polymerization inhibitor (I4) contained in the curable resin composition of the present invention is 0. 0 based on the weight of the curable resin composition from the viewpoint of storage stability and polymerization rate of the curable resin composition. The content is preferably 01 to 5% by weight, more preferably 0.05 to 3%.

  The curable resin composition of the present invention preferably contains a surfactant (I7) as necessary from the viewpoint of applicability to a resin substrate.

  Surfactant (I7) contained for this purpose includes PEG type nonionic surfactants [nonylphenol EO 1-40 mol adduct, stearic acid EO 1-40 mol adduct, etc.], polyhydric alcohol type nonionic surfactant Agents (sorbitan palmitic acid monoester, sorbitan stearic acid monoester, sorbitan stearic acid triester, etc.), fluorine-containing surfactants (perfluoroalkyl EO 1-50 mol adducts, perfluoroalkyl carboxylates, perfluoroalkyl betaines, etc.) And polysiloxanes partially modified with substituents (such as polyether groups).

  The weight ratio of the surfactant (I7) contained in the curable resin composition of the present invention is determined from the viewpoint of adjusting the surface tension of the curable resin composition and the contact angle of the cured product of the curable resin composition with water. 0.1 to 10% based on the weight of the conductive resin composition, preferably 0.1 to 8% by weight.

  The weight ratio of the ethylenically unsaturated monomer (A) having a urethane group contained in the curable resin composition of the present invention is 10 to 50% by weight based on the total weight of (A) to (C). It is preferably 20 to 40% by weight.

  The weight ratio of the monofunctional ethylenically unsaturated monomer (B) having no urethane group contained in the curable resin composition of the present invention is 10 to 70 weight based on the total weight of (A) to (C). %, More preferably 20 to 60% by weight, and particularly preferably 30 to 50% by weight.

  The weight ratio of the polyfunctional ethylenically unsaturated monomer (C) having no urethane group contained in the curable resin composition of the present invention is based on the total weight of (A) to (C) from the viewpoint of toughness. It is preferably 10 to 50% by weight, and more preferably 15 to 35% by weight.

  The weight ratio of the silane compound (D) contained in the curable resin composition of the present invention is 0.1 to 10 weights based on the total weight of (A) to (C) from the viewpoint of adhesion to the substrate. %, More preferably 3 to 5% by weight.

  From the viewpoint of curability, the weight ratio of the photopolymerization initiator (E) contained in the curable resin composition of the present invention is 0.5 to 10% by weight based on the total weight of (A) to (C). Preferably, it is 0.8 to 8% by weight, more preferably 1.0 to 8% by weight.

  The weight ratio of (F) contained in the curable resin composition of the present invention is 0.5 to 10% by weight based on the weight of (A) to (C) from the viewpoint of adhesion of the cured product. Is more preferable, and 1.0 to 5.0% by weight is more preferable.

  The weight ratio of (G) contained in the curable resin composition of the present invention is 0.5 to 10% by weight based on the weight of (A) to (C) from the viewpoint of the adhesion of the cured product. Is more preferable, and 1.0 to 5.0% by weight is more preferable.

  From the viewpoint of mold releasability, the weight ratio of the phosphate ester and amine salt (H) contained in the curable resin composition of the present invention is 0 based on the total weight of (A) to (C). It is preferably 0.01 to 1.0% by weight, more preferably 0.02 to 0.8% by weight, and particularly preferably 0.05 to 0.5% by weight.

  The curable resin composition of the present invention is prepared by, for example, performing the above-mentioned (A) to (E) and, if necessary, the above (F) to (I), a known mechanical mixing method (mechanical stirrer, magnetic stirrer, etc. It can be manufactured by uniformly mixing using the method used.

As described above, the silane compound (D) is preferably the silane compound (D1) in which X is a (meth) acryloyloxyalkyl group in the general formula (1), and the ethylenically unsaturated group. As the monomer (F), a vinyl monomer having a phosphate group and a vinyl monomer having a phosphate ester group are preferable.
The weight ratio of the silane compound (D1) to the total weight of the vinyl monomer having a phosphate group and the vinyl monomer having a phosphate ester group [weight of the silane compound (D1) / the phosphate group From the viewpoint of the toughness of the cured product, the total weight of the vinyl monomer having a vinyl group and the vinyl monomer having a phosphate group] is preferably 2.8 to 2.2, and more preferably 2.7 to 2.3. And particularly preferably 2.6 to 2.4.

The curable resin composition of this invention can manufacture the molded object which can be used as an optical component by hardening.
Below, the method to harden the curable resin composition of this invention and manufacture a molded object is demonstrated.
The method for producing a molded body using the curable resin composition of the present invention is not particularly limited, but when producing a three-dimensional plastic lens having a fine concavo-convex structure, for example, a flat having a fine concavo-convex structure is provided. It can be obtained by photocuring the curable resin composition using a mold and releasing from the mold.

The following method etc. are mentioned as a more concrete manufacturing method of a molded object.
A mold (mold temperature is preferably 20 to 50 ° C., more preferably 25 to 40 ° C.) in which the temperature of the resin composition of the present invention is adjusted in advance to 20 to 50 ° C. to obtain a molded body shape (for example, optical lens shape) Using a dispenser, etc., apply (or fill) the cured film to a thickness of 20 to 150 μm, and pressurize and laminate the transparent substrate (including the transparent film) from above the coating film. To do.
And an active energy ray is irradiated from the said transparent base material, and this coating film is hardened. In addition, when it contains a thermal polymerization initiator (C2) as a radical polymerization initiator (C), this coating film can be hardened also by heating to 50-250 degreeC.
Thereafter, the cured product is released from the mold to obtain a molded body (lens sheet).

  Examples of the transparent substrate (including a transparent film) include those formed using a resin such as methyl methacrylate (co) polymer, polyethylene terephthalate, polycarbonate, triacetyl cellulose, and polycycloolefin.

Examples of active energy rays in the present invention include heat rays, actinic rays, and electron beams.
In the present invention, the active light means ultraviolet light having a wavelength of 250 nm to 830 nm.
When the resin composition of the present invention is cured with an active energy ray, various active energy ray irradiation devices [for example, an active energy ray irradiation device [model number “VPS / I600” manufactured by Fusion UV Systems Co., Ltd.] can be used. .
Examples of the lamp used include a high-pressure mercury lamp and a metal halide lamp.
The dose of active energy rays, preferably a flexible viewpoint of curability and cured product of a composition 10~10,000mJ / cm ^2, more preferably from 100~5,000mJ / cm ^2.

  Since the cured product of the curable resin composition of the present invention is excellent in mold releasability, adhesion, low warpage, and toughness, it is useful as an optical member and an electric / electronic member.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

Moreover, Mn of the urethane (meth) acrylates (A-1) to (A-5) synthesized in Production Examples 1 to 5 was measured by GPC under the following conditions.
[1] Apparatus: Gel permeation chromatography “HLC-8120GPC”, manufactured by Tosoh Corp. [2] Column: “TSKgel GMHXL” x 2 + “TSKgel Multipore HXL-M”, manufactured by Tosoh Corp. [3] Eluent: Tetrahydrofuran [4] Reference material: Standard polystyrene (TSK standard POLYSTYRENE), manufactured by Tosoh Corporation [5] Injection conditions: Sample concentration 0.25 wt%, column temperature 40 ° C.
In Production Examples 1 to 5, the isocyanate content represents the weight of the isocyanate group remaining in the sample as a weight ratio with respect to the weight of the sample, and the isocyanate group content (%) described in JIS K 1603-1. ) Was measured according to the measurement method.

Production Example 1 [Production of Ethylenically Unsaturated Monomer (A-1) Having Urethane Group]
In a glass reaction vessel equipped with a stirrer and a thermometer, a PO2 molar adduct of bisphenol A [trade name: New Pole BP-2P, manufactured by Sanyo Chemical Industries, Ltd.] 57.0 parts, 4,4′- 48.1 parts of MDI [trade name: Takenet 300, manufactured by Takeda Pharmaceutical Co., Ltd.], and 0.5 parts of a 50% 2-ethylhexanoic acid solution of bismuth tri (2-ethylhexanoate) as a catalyst After stirring to obtain a homogeneous solution, the temperature was raised to 80 ° C. While adjusting the temperature in the container to 80 ° C., the first-stage urethanization reaction was performed for 6 hours.
After confirming that the isocyanate content was 2.29% or less, 2-hydroxyethyl was introduced while a nitrogen / oxygen mixed gas having an oxygen concentration adjusted to 8% by volume for the purpose of inhibiting polymerization was passed through the liquid. 6.6 parts of acrylate was added, and the second urethanization reaction was performed at 75 ° C. for 2 hours.
After confirming that the isocyanate content was 0.01% or less, the mixture was cooled to 60 ° C. to obtain an ethylenically unsaturated monomer (A-1) having a urethane group in the present invention. The Mn of (A-1) was 2,900.

Production Example 2 [Production of Ethylenically Unsaturated Monomer (A-2) Having Urethane Group]
In Production Example 1, bisphenol A PO 2 mol adduct was added to 73.5 parts of bisphenol A EO 10 mol adduct [trade name: New Pole BPE-100, manufactured by Sanyo Chemical Industries, Ltd.], 4,4′-MDI. Was changed to TDI [trade name: Takenate 80, Takeda Pharmaceutical Co., Ltd.] 22.2 parts, and the number of parts of 2-hydroxyethyl acrylate was changed to 4.3 parts. The ethylenically unsaturated monomer (A-2) which has a urethane group in this invention by operation was obtained. Mn of (A-2) was 4,600.

Production Example 3 [Production of Ethylenically Unsaturated Monomer (A-3) Having Urethane Group]
In Production Example 1, the number of parts of PO2 molar adduct of bisphenol A was 51.0 parts, and 4,4′-MDI was XDI [trade name: Takenet 500, manufactured by Takeda Pharmaceutical Co., Ltd.] 37.1 The ethylenically unsaturated monomer (A-3) having a urethane group in the present invention was obtained in the same manner as in Production Example 1, except that the number of parts of 2-hydroxyethyl acrylate was changed to 11.8 parts. It was. Mn of (A-3) was 1,500.

Production Example 4 [Production of Ethylenically Unsaturated Monomer (A-4) Having Urethane Group]
In Production Example 1, the PO2 molar adduct of bisphenol A is 55.6 parts, and 4,4'-MDI is hexamethylene diisocyanate [trade name: Duranate 50M, manufactured by Asahi Kasei Chemicals] 34.2 parts. An ethylenically unsaturated monomer (A-4) having a urethane group was obtained in the same manner as in Production Example 1, except that the number of parts of 2-hydroxyethyl acrylate was changed to 10.2 parts. Mn of (A-4) was 1,800.

Production Example 5 [Production of Ethylenically Unsaturated Monomer (A-5) Having Urethane Group]
In Production Example 1, PO2 mol adduct of bisphenol A was added to 65.0 parts of polytetramethylene glycol [trade name: PTMG-1000, manufactured by Mitsubishi Chemical Corporation], and 4,4′-MDI was added to dicyclohexylmethane diisocyanate [product]. Name: Desmodur W, manufactured by Sumika Bayer Urethane Co., Ltd.] 26.6 parts, except that the number of parts of 2-hydroxyethyl acrylate was changed to 8.4 parts, the urethane group was the same as in Production Example 1 The ethylenically unsaturated monomer (A-5) was obtained. Mn of (A-5) was 2,200.

Production Example 6 [Production of phosphate ester and amine salt (H-1)]
In a glass reaction vessel equipped with a stirrer and a thermometer, 55.6 parts of 2-ethylhexyl alcohol phosphate ester [trade name “AP-8”, manufactured by Daihachi Chemical Co., Ltd.] was charged. 44.4 parts of N, N-dimethylstearylamine [trade name “Farmin DM8098” manufactured by Kao Co., Ltd.] was added thereto and stirred at 50 ° C. for 2 hours, and 2-ethylhexyl alcohol phosphate ester and N, N -A salt (H-1) of dimethylstearylamine was obtained.

Production Example 7 [Production of phosphate ester and amine salt (H-2)]
Manufacture except that in Example 6, the phosphate ester of 2-ethylhexyl alcohol was changed to 55.6 parts of phosphate ester of tridecanol EO 10 mol adduct [trade name “IONET 1310R”, manufactured by Sanyo Chemical Industries, Ltd.] The alkylamine salt (H-2) of the phosphate ester of the present invention was obtained in the same manner as in Example 6.

Examples 1-6, Comparative Examples 1-4
It mixed at 80 degreeC by the compounding composition (weight part) shown in Table 1, and obtained the curable resin composition of Examples 1-6 and the comparative curable resin composition of Comparative Examples 1-4.

The contents indicated by the symbols in Table 1 are as follows.
(B-1): benzyl acrylate [trade name “Fancryl FA-BZA”, manufactured by Hitachi Chemical Co., Ltd., functional group number 1]
(B-2): Isobornyl acrylate [trade name “light acrylate IBXA”, manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups 1]
(B-3): Dicyclopentanyl acrylate [trade name “Fancryl FA-513A”, manufactured by Hitachi Chemical Co., Ltd., number of functional groups 1]
(B-4): 1-adamantyl acrylate [trade name “1-AdA”, manufactured by Osaka Organic Chemical Industry Co., Ltd., number of functional groups 1]
(B-5): Acryloylmorpholine [trade name “ACMO”, manufactured by KJ Chemicals, Inc., functional group number 1]
(B-6): Phenoxyethyl acrylate [trade name “Biscoat # 192, PEA”, manufactured by Osaka Organic Chemical Industry Co., Ltd., number of functional groups 1]

(C-1): Diacrylate of EO4 mol adduct of bisphenol A [trade name “Neomer BA-641”, manufactured by Sanyo Chemical Industries, Ltd., functional group number 2]
(C-2): dimethylol tricyclodecane diacrylate [trade name “light acrylate DCP-A”, manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups 2]
(C-3): Diacrylate of EO 20 mol adduct of bisphenol A [trade name “NK ester A-BPE-20”, manufactured by Shin-Nakamura Chemical Co., Ltd., functional group number 2]

(D-1): 3-acryloyloxypropyltrimethoxysilane [trade name “KBM-5103”, manufactured by Shin-Etsu Chemical Co., Ltd.]
(D-2): 3-Methacryloyloxypropyltrimethoxysilane [trade name “KBM-503”, manufactured by Shin-Etsu Chemical Co., Ltd.]
(D-3): N- (1,3-dimethyl-butylidene) -3-triethoxysilylpropylamine [trade name “KBE-9103”, manufactured by Shin-Etsu Chemical Co., Ltd.]

(E1-1): 1-hydroxycyclohexyl phenyl ketone [trade name “Irgacure 184”, manufactured by BASF Corporation]
(E1-2): 2,4,6-trimethylbenzoyldiphenylphosphine oxide [trade name “Irgacure TPO”, manufactured by BASF Corporation]
(E1-3): Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide [trade name “Irgacure 819”, manufactured by BASF Corporation]
(E1-4): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one [trade name “Irgacure 907”, manufactured by BASF Corporation]
(E2-1): Di-t-butyl peroxide [trade name “Perbutyl D”, manufactured by NOF Corporation]

(F-1): caprolactone-modified [2-{(meth) acryloyloxy} ethyl] acid phosphate [trade name “KAYAMER PM-21”, manufactured by Nippon Kayaku Co., Ltd.]
(F-2): 2-acryloyloxyethyl hexahydrophthalic acid [trade name “Light Acrylate HOA-HH (N)”, manufactured by Kyoeisha Chemical Co., Ltd.]

(G-1): Dibutyl phosphate [trade name “DBP”, manufactured by Johoku Chemical Co., Ltd.]

(I-1): Pentaerythritol tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate [trade name “IRGANOX1010”, manufactured by BASF Japan Ltd.] (antioxidant)
(I-2): 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and oxirane [(10 to 16 carbon atoms) Product of alkyloxy) methyl] oxirane / 1-methoxy-2-propanol = 85/15 (weight ratio) [trade name “TINUVIN400”, manufactured by BASF Japan Ltd.] (UV absorber)
(I-3): Phenothiazine [Wako Pure Chemical Industries, Ltd.] (polymerization inhibitor)
(I-4): Hydroquinone monomethyl ether [Wako Pure Chemical Industries, Ltd.] (polymerization inhibitor)

About the curable resin composition of Examples 1-6 and the comparative curable resin composition of Comparative Examples 1-4, mold release property of the cured product, adhesion to the resin base material, low warpage, tensile fracture Strength, fracture energy, and toughness were measured by the following methods.
The results are shown in Table 1.

(1) Mold releasability (i)
A curable resin composition was applied to the surface of a SUS mold that had a groove depth of 200 μm and a pitch width of 80 μm in parallel, and was finely textured to a thickness of 100 μm. Thereafter, a PET film having a thickness of 100 μm [trade name “Cosmo Shine A4300” manufactured by Toyobo Co., Ltd.] was placed on the coated surface, and the rollers were rolled from above to extrude air and bonded together.
(Ii-1) In the case of Example 1 It heated at 100 degreeC for 10 minute (s), the curable resin composition was hardened, and the cured film was created. The cured film adhered to the base film was peeled off from the plate glass, and it was judged with a laser microscope whether or not the uneven transfer was reproduced.
(Ii-2) In the case of Examples 2 to 6 and Comparative Examples 1 to 4, the active energy ray was 1000 mJ from the PET film side using an active energy ray irradiation device [model number “VPS / I600”, manufactured by Fusion UV Systems Co., Ltd.]. / Cm ^{2 was} irradiated to cure the curable resin composition, and a cured film was formed. The cured film in close contact with the film was peeled off from the mold, and it was determined with a laser microscope whether the uneven transfer was reproduced.

Judgment criteria are as follows.
A: There is no resin residue on the mold, the uneven transfer can be reproduced, and the mold is smoothly separated.
○: There is no resin residue on the mold, and the uneven transfer can be reproduced.
X: Resin remains in the mold, and uneven transfer cannot be reproduced.

(2) Adhesiveness to resin substrate In accordance with JIS K 5600-5-6, 25 (5 × 5) squares of the cured product peeled from the mold in the mold releasability evaluation described above A 2 mm width was cut with a cutter knife so that the adhesion was measured.

Judgment criteria are as follows.
○: 25 squares remained on the film after the test.
X: 24 or less squares remained on the film after the test.
−: Tests with mold release characteristics of “x” could not be tested.

(3) Low warpage (i)
After coating the surface of the glass plate with a curable resin composition so as to have a thickness of 10 μm, a PET film having a length of 100 mm or more, a width of 100 mm or more and a thickness of 100 μm [trade name “Cosmo Shine A4300” Toyobo ( Co., Ltd.] was placed on the coated surface, and the roller was rolled from above to extrude air and bonded together.
(Ii-1) In the case of Example 1 The curable resin composition was cured by heating at 100 ° C. for 10 minutes.
(Ii-2) In the case of Examples 2 to 6 and Comparative Examples 1 to 4 The active energy ray is irradiated from the PET film side by the above active energy ray irradiator at 1000 mJ / cm ² to cure the curable resin composition. I let you.
(Iii)
The cured product was peeled off from the glass plate to prepare a cured film for test evaluation (a PET film as a base material coated with a cured product of each curable resin composition).
The prepared cured film was cut into a square of 100 mm length × 100 mm width and temperature-controlled at room temperature for 1 hour.
Thereafter, the warp levels at the four corners of the cured film were measured using a gap (thickness) gauge, thereby evaluating the test sample for warp characteristics.
○: All four of the four corners are 30 mm or less.
X: One of the four corner warps that is larger than 30 mm.

(4) Tensile strength at breaks Using a tensile tester [manufactured by Shimadzu Corporation] according to JIS K7161, using a cured product of the curable resin composition as a test piece (small test piece 5A type), a test speed of 50 mm The tensile strength at break (N / mm ² ) was measured.

(5) Fracture energy In the measurement at the above-mentioned (4) tensile breaking strength, the energy applied until the fracture occurred was determined from the area of the stress-strain curve until the fracture, and was defined as the fracture energy (J).

(6) Toughness From the above (4) tensile fracture strength and (5) fracture energy values, the toughness was comprehensively determined according to the following criteria.
○: Tensile breaking strength is 20 N / mm ² or more and breaking energy is 3.0 J or more Δ: Tensile breaking strength is 20 N / mm ² or more and breaking energy is 2.0 J or more ×: Tensile breaking strength is less than 20 N / mm ² or Breaking energy less than 2.0J

From the results of Table 1, the cured products of the curable resin compositions of Examples 1 to 6 are excellent in all of mold releasability, adhesion to a resin substrate, low warpage, and toughness. I understand that.
On the other hand, the comparative curable resin composition of Comparative Example 1 which does not contain an ethylenically unsaturated monomer (A) having a urethane group has poor toughness. The comparative curable resin composition of Comparative Example 2 that does not contain the monofunctional ethylenically unsaturated monomer (B) having no urethane group has poor adhesion to the resin substrate and large warpage. The comparative curable resin composition of Comparative Example 3 containing no polyfunctional ethylenically unsaturated monomer (C) having no urethane group has poor mold releasability and insufficient toughness. The comparative curable resin composition of Comparative Example 4 that does not contain the silane compound (D) having a specific chemical structure has poor adhesion to the resin substrate.

Since the curable resin for optical components of the present invention is excellent in mold releasability, adhesion, low warpage and toughness, it is also useful as an optical member and an electric / electronic member.
In addition, the optical component using the cured product of the present invention is used in the form of a film or a sheet, as well as a plastic lens (prism lens, lenticular lens, microlens, Fresnel lens, viewing angle control lens, contrast enhancement lens, etc.), It is extremely useful as a retardation film, electromagnetic wave shielding film, prism, optical fiber, flexible printed wiring solder resist, plating resist, multilayer printed wiring board interlayer insulating film, and photosensitive optical waveguide.

Claims (11)

Ethylenically unsaturated monomer having urethane group (A), monofunctional ethylenically unsaturated monomer having no urethane group (B), polyfunctional ethylenically unsaturated monomer having no urethane group (C) A curable resin composition containing a silane compound (D) represented by the following general formula (1) and a radical polymerization initiator (E).

[In General Formula (1), R ¹ O represents an alkoxy group having 1 to 4 carbon atoms; X represents an alkyl group, a (meth) acryloyloxyalkyl group, an aminoalkyl group, a vinyl group, or a glycidoxyalkyl. Group, vinylphenyl group, isocyanate alkyl group, isocyanurate group, ureidoalkyl group or mercaptoalkyl group; when there are plural groups, R ¹ O and X may be the same or different; n is an integer of 1 to 3 It is. ]   The curable resin composition according to claim 1, wherein the ethylenically unsaturated monomer (A) having a urethane group contains at least one (meth) acryloyl group.   The curable resin composition according to claim 1 or 2, wherein the monofunctional ethylenically unsaturated monomer (B) having no urethane group has one (meth) acryloyl group.   The curable resin composition according to any one of claims 1 to 3, wherein the polyfunctional ethylenically unsaturated monomer (C) having no urethane group has 2 to 6 (meth) acryloyl groups. .   The silane compound (D) is a silane compound (D1) in which X is a (meth) acryloyloxyalkyl group in the general formula (1) and / or a silane in which X is an aminoalkyl group in the general formula (1). The curable resin composition of any one of Claims 1-4 containing a compound (D2).   Furthermore, it contains an ethylenically unsaturated monomer (F) having at least one functional group (a) selected from the group consisting of a carboxy group, a phosphate group, a phosphate ester group and a sulfo group. The curable resin composition according to any one of 5.   Furthermore, any one of Claims 1-6 containing the at least 1 sort (s) of organic acid ester compound (G) chosen from the group which consists of phosphate ester (G1), carboxylic acid ester (G2), and sulfonate ester (G3). The curable resin composition according to Item 1.   The curable resin composition according to claim 7, wherein the organic acid ester compound (G) is a phosphate ester (G1).   The weight ratio of the monofunctional ethylenically unsaturated monomer (B) having no urethane group is such that the ethylenically unsaturated monomer (A), the ethylenically unsaturated monomer (B) and the ethylenically unsaturated monomer The curable resin composition according to any one of claims 1 to 8, which is 10 to 70% by weight based on the total weight with the saturated monomer (C).   It is for optical components, The curable resin composition of any one of Claims 1-9. Hardened | cured material formed by hardening | curing the curable resin composition of any one of Claims 1-10.