JP6643846B2 - Polyurethane compound and resin composition containing the same - Google Patents

Description

  The present invention relates to a resin composition containing a urethane (meth) acrylate having a hydrogenated polybutadiene polyol as a main skeleton. Further, the cured film of the resin composition of the present invention is excellent in flexibility, transparency, moisture resistance, adhesion to a substrate, and has little curing shrinkage, and is particularly useful as a bonding application for an optical film of a display device. is there.

  BACKGROUND ART Conventionally, urethane (meth) acrylate, which is a reaction product of a polyol compound, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound, has been widely used as a coating agent, an adhesive, a photoresist and the like. For example, in fields where deterioration due to yellowing is a problem, particularly in optical applications such as Patent Document 1, urethane (meth) acrylate compounds are designed based on highly transparent polyol compounds and aliphatic or alicyclic polyisocyanates. I do.

  In some cases, hydrogenated polybutadiene is selected as a polyol compound to improve its yellowing or weather resistance when exposed to severe conditions, and its characteristics are sometimes brought out. In Patent Document 2, urethane (meth) acrylate is produced using hydrogenated polybutadiene polyol. Although the cured product has excellent weather resistance, it has very high hydrophobicity as a hydrogenated polybutadiene skeleton, and is considered to have limited compatibility with monomers and additives that can be blended as a composition. In addition, the hydrogenated polybutadiene polyol used has a relatively high iodine value, which suggests that it may not provide properties satisfying the currently required weather resistance and light resistance. Furthermore, since it is manufactured without dilution as a urethane (meth) acrylate resin, there is a possibility that there is a problem in terms of workability due to high viscosity in actual industrialization.

  In recent years, urethane (meth) acrylates have been actively studied and commercialized for LCD (liquid crystal display) applications. For example, Patent Document 3 discloses a photocurable adhesive composition used for bonding an optical display or a touch sensor using a polybutadiene-based (meth) acrylate oligomer and a urethane (meth) acrylate oligomer. It is presumed that urethane (meth) acrylate, which has excellent flexibility and higher weather resistance and light resistance, will be required in the future. Patent Document 4 describes application of urethane (meth) acrylate to a LCD optical member using a polyol compound having no aromatic ring.

  In particular, in the application of bonding of a capacitive touch panel, it is one of the mainstream methods at present to characterize by utilizing the flexibility characteristic of urethane (meth) acrylate. Also describes use examples of urethane (meth) acrylate. When used in such applications, flexibility needs to be better and urethane (meth) acrylate having a high molecular weight needs to be applied. However, in general, when the molecular weight of urethane (meth) acrylate is increased, flexibility can be improved, but toughness tends to be reduced, and as a result, the adhesive strength is generally reduced as a result.

Japanese Patent No. 2582575 Japanese Patent No. 4868654 JP 2012-46658 A JP 2011-190421 A JP-A-2015-67777

  Urethane (meth) acrylates are required to have higher weather resistance, higher light resistance and improved physical properties of cured films, as well as improved compatibility with other resins, monomers, and additives. In addition, in the case of a touch panel adhesive application, flexibility that affects bonding condition and step followability and high adhesive strength that affects peeling are required.

  The present invention improves the above requirements, provides a cured film having excellent weather resistance and light resistance, and has excellent flexibility, has a low shrinkage ratio upon curing, and provides a resin composition having high adhesive strength. Aim.

  Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a resin composition having a specific compound and composition can solve the above problems, and have reached the present invention.

That is, the present invention
(1) Polyurethane compound (F) which is a reaction product of compound (A) shown below, compound (B), compound (C) and compound (D),
Compound (A): hydrogenated polybutadiene polyol compound Compound (B): diol compound having an alicyclic skeleton
Compound (C): polyisocyanate compound Compound (D): (meth) acrylate compound having at least one or more hydroxyl groups
Compound (E): a polyol compound other than compound (A) and compound (B)
(2) Polyurethane compound (F) which is a reaction product of compound (A) shown below with compound (B), compound (C), compound (D) and compound (E);
Compound (A): hydrogenated polybutadiene polyol compound Compound (B): diol compound having an alicyclic skeleton
Compound (C): polyisocyanate compound Compound (D): (meth) acrylate compound having at least one or more hydroxyl groups
Compound (E): a polyol compound other than compound (A) and compound (B)
(3) The polyurethane compound (F) according to (1) or (2), wherein the hydrogenated polybutadiene polyol compound (A) has an iodine value of 20 or less,
(4) The polyurethane compound (F) according to any one of (1) to (3), wherein the diol compound (B) having an alicyclic skeleton is a diol compound having an alicyclic structure having 20 or less carbon atoms.
(5) The polyurethane compound (F) according to any one of (1) to (4), wherein the diol compound (B) having an alicyclic skeleton is tricyclodecane dimethanol.
(6) The polyurethane compound (F) according to any one of (1) to (5), wherein the polyisocyanate compound (C) is an aliphatic diisocyanate compound.
(7) The polyurethane compound (F) according to any one of (1) to (6), wherein the (meth) acrylate compound (D) having at least one or more hydroxyl groups is 2-hydroxyethyl (meth) acrylate.
(8) A photosensitive resin composition comprising the polyurethane compound (F) according to any one of (1) to (7) and a polymerizable compound (G) other than (F).
(9) The photosensitive resin composition according to (8), wherein the polymerizable compound (G) is an alkyl (meth) acrylate or an alkylene (meth) acrylate.
(10) The photosensitive resin composition according to (8) or (9), which contains a photopolymerization initiator (H),
(11) A cured product of the photosensitive resin composition according to any one of (8) to (10),
(12) The photosensitive resin composition for a filler in a gap between a display device and a surface plate according to any one of (1) to (11),
(13) A touch panel including the cured product layer of the filler according to (12),
About.

The cured film of the photosensitive resin composition containing the polyurethane compound of the present invention has excellent adhesiveness to the substrate, excellent flexibility, high weather resistance, high light resistance, and other than optical member applications in which transparency needs to be maintained. Ink, plastic paint, paper printing, metal coating, furniture coating, various coating fields, linings, adhesives, insulating varnishes, insulating sheets, laminates, printed boards, resist inks, semiconductor encapsulants in the electronics field It can be applied to many fields such as an air gap filler for a display device such as a touch panel type image display device (a filler for a gap between a display device and a surface plate).

  The polyurethane compound (F) of the present invention comprises a hydrogenated polybutadiene polyol compound (A) and a diol compound (B) having an alicyclic skeleton, and if necessary, a compound (A) other than the compound (B). And the polyisocyanate compound (C) are first reacted (hereinafter referred to as the first reaction of the present invention), and then the (meth) acrylate compound (D) having at least one or more hydroxyl group with respect to the remaining isocyanate group is obtained. Reaction (hereinafter, referred to as the second reaction of the present invention).

The hydrogenated polybutadiene polyol compound (A) used in the first reaction of the present invention can be used as long as it is a hydrogenated reduction product of a general polybutadiene polyol, but particularly has little residual double bonds for optical applications. The iodine value is more preferably 20 or less, and particularly preferably 15 or less. As for the molecular weight of (A), any of those having a molecular weight distribution generally available can be used. Particularly, when the flexibility and the curability are balanced, those having a number average molecular weight of 500 to 5,000 are preferable, Those with 500 to 3000 are particularly preferred.
Commercially available hydrogenated polybutadiene polyol compounds (A) include, for example, GI-1000, GI-2000, GI-3000 manufactured by Nippon Soda Co., Ltd., KRASOL HLBP-H1000, HLBP-H2000, HLBP- manufactured by CRAY VALLEY. H 3000 and the like.

Specific examples of the diol compound (B) having an alicyclic skeleton used in the first reaction of the present invention include, for example, cyclohexane dimethanol, norbornane dimethanol, norbornene dimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethyl Examples include methanol, adamantane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated terpene diphenol, and EO, PO, and caprolactone modified products thereof. In the photosensitive resin composition of the present invention, it is preferable to use an alicyclic structure having 20 or less carbon atoms in order to particularly improve the adhesive properties. In particular, from the viewpoint of workability such as improvement of wet heat resistance and viscosity, tricyclode. It is preferred to use candimethanol. Commercial products of tricyclodecane dimethanol include, for example, TCD alcohol DM of Celanese Corporation.
Further, a diol compound having a bridged structure such as norbornane dimethanol, norbornene dimethanol, tricyclodecane dimethanol, and adamantane dimethanol is preferable from the viewpoint of improving water resistance.

Here, in the present invention, when the hydrogenated polybutadiene polyol compound (A) and the diol compound (B) having an alicyclic skeleton are used in the reaction, the usage ratio of the hydrogenated polybutadiene (A) and the alicyclic skeleton (B) is as follows. Although not particularly limited, the molar ratio of component (A): component (B) is preferably 9.9: 0.1 to 0.1: 9.9, and 9.5: 0.5 to 0.5: 9.9. 5 is more preferable, and 9.0: 1.0 to 1.0: 9.0 is particularly preferable.

Specific examples of the polyol compound (E) other than the compound (A) and the compound (B) used as an optional component in the first reaction of the present invention include, for example, polyethylene glycol, polybutylene glycol, polytetramethylene glycol, and polypropylene. Glycols, polyether polyols such as polyethylene glycol, polyethylene glycol adipate, polyester polyols such as poly-1,4-butanediol adipate, polycaprolactone, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and neopentyl glycol Glycol, cyclohexane dimethylol, hydrogenated bisphenol A, hydrogenated bisphenol F, spiro skeleton-containing alcohol, tricyclodecane dimethylol and pen Alicyclic alcohols such as cyclopentadecane dimethylol and alkylene oxide adducts thereof, branched or linear long-chain alkyl diols such as diols of hydrogenated polybutadiene, bisphenols such as bisphenol A and bisphenol F, and alkylene oxides of bisphenol Adducts, polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol, and alkylene oxide adducts of these polyols, and also polyester polyols obtained by reacting these polyols with polybasic acids such as adipic acid And the like. Although there is no particular limitation, the use of polyether polyols is particularly preferred for improving flexibility and compatibility in the cured product of the photosensitive resin composition of the present invention. Further, polypropylene polyol is preferable because it can exert an effect of suppressing whitening of the resin layer.
With respect to the molecular weight of such a polyol compound (E), any of those having a molecular weight distribution generally available can be used, but especially those having a number average molecular weight of 100 to 6,000 when flexibility and curability are balanced. Are preferred, and those with 200 to 4000 are particularly preferred.
In consideration of compatibility with other monomers while maintaining transparency and light resistance, the polyol compound (E) particularly preferably used is a polyether polyol having a number average molecular weight of 200 to 4,000.

Here, in the present invention, when a polyol compound (E) other than the compound (A) and the compound (B) is used in the reaction as an optional component, the use of the compound (A) and the compound (B) and the polyol compound (E) is used. Although the ratio is not particularly limited, the molar ratio of the component (A + B): the component (E) is preferably 9.999: 0.001 to 2: 8, more preferably 9.999: 0.001 to 3: 7, and 9 .999: 0.001 to 4: 6.

  The polyisocyanate compound (C) used in the first reaction of the present invention is a compound containing two or more isocyanate groups in one molecule, such as an aliphatic diisocyanate compound and an aromatic diisocyanate compound. And trimeric compounds thereof. The aliphatic diisocyanate compound referred to herein means a diisocyanate compound having an isocyanate group bonded to a chain carbon atom and a diisocyanate compound having an isocyanate group bonded to a carbon atom of a cyclic saturated hydrocarbon, and an aromatic diisocyanate compound. Means a diisocyanate compound in which an isocyanate group is bonded to a carbon atom of an aromatic ring.

  Examples of the aliphatic diisocyanate compound include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-diisocyanate cyclohexane, and 1,4-diisocyanate Cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, m-tetramethylxylene diisocyanate, p-tetramethylxylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4-trimethylcyclohexane Diisocyanate, 2,4,4-trimethylcyclohexane diisocyanate, 2,2,4-trimethylhexamethylene diisocy Sulfonate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate and the like.

  Examples of the aromatic diisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,6-phenylene diisocyanate, 1,4-phenylene diisocyanate, and 1,6-phenylene. And diisocyanate monomers such as diisocyanate.

  Among these, an aliphatic diisocyanate compound and a trimer of the aliphatic diisocyanate compound are preferable for improving the weather resistance of the coating film. Examples of the trimer of the aliphatic diisocyanate compound include the above-mentioned aliphatic isocyanate-based isocyanurate-type polyisocyanate, and specific examples thereof include hexamethylene diisocyanate and isophorone diisocyanate. These may be used alone or in a mixture.

In the present invention, the first reaction is charged in an equivalence relation ((C) / (A + B + (E))> 1: [NCO] / [OH] molar ratio such that the isocyanate group remains after the reaction. When the charge ratio is increased, many unreacted polyisocyanate compounds are present, which may affect the flexibility of the photosensitive resin composition. In addition, when the charge ratio is reduced, the molecular weight increases, which may affect the curability of the photosensitive resin composition. Specifically, preferably, the OH group of the alcohol compound (A + B + (E)) is 0.1 to 0.9 mol with respect to 1.0 mol of the NCO group of the polyisocyanate compound (C).
Here, in the above calculation formula, (E) is the above notation because the component (E) is an optional component, and when it is contained, it is included in the above calculation formula, but when it is not contained, it is calculated as 0. .

  In the present invention, the first reaction can be carried out without a solvent. However, in order to improve the workability due to a high viscosity of the product, the first reaction is carried out in a solvent having no alcoholic hydroxyl group described below or a polymerizable compound ( It is preferably carried out in G). Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dipropylene glycol. Glycol ethers such as dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, Esters such as propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. In a single or mixed organic solvent.

  The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is confirmed by a decrease in the amount of isocyanate. Further, a catalyst may be added for the purpose of shortening the reaction time. As this catalyst, either a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine, and ammonia, and phosphines such as tributylphosphine and triphenylphosphine. Examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, aluminum tributoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, aluminum chloride, tin octylate, octyltin trilaurate, dibutyltin dilaurate, Lewis acid catalysts such as octyltin diacetate can be mentioned. The addition amount of these catalysts is usually 0.1 to 1 part by weight based on 100 parts by weight of the total weight of the diol compound (A + B + (E)) and the isocyanate compound (C).

  After the first reaction, the polyurethane compound (F) of the present invention is obtained by subsequently reacting the (meth) acrylate compound (D) having at least one or more hydroxyl groups with respect to the remaining isocyanate groups (second reaction). be able to.

The (meth) acrylate compound (D) having at least one hydroxyl group used in the second reaction of the present invention is a compound having at least one hydroxyl group and at least one (meth) acryloyl group in one molecule. Yes, specifically, 2-hydroxyethyl (meth) acrylate, propylene glycol mono (meth) acrylate, butanediol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, diethylene glycol mono (Meth) acrylate, dipropylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene Glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, ethoxylated neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate. Mono (meth) acrylates of polyhydric alcohols;

Trimethylolpropane mono (meth) acrylate, ethoxylated trimethylolpropane mono (meth) acrylate, propoxylated trimethylolpropane mono (meth) acrylate, tris (2-hydroxyethyl) isocyanurate mono (meth) acrylate, glycerin mono (meth) A) acrylate, trimethylolpropanedi (meth) acrylate, ethoxylated trimethylolpropanedi (meth) acrylate, propoxylated trimethylolpropanedi (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, glycerin Monohydric and di (meth) acrylates of trihydric alcohols such as di (meth) acrylate and the like, and some of the hydroxyl groups of these alcohols are substituted with alkyl groups or ε-caprolactone Modified mono- and di (meth) acrylate;

Pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, ditrimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, ditrimethylolpropanedi (meth) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa Polyfunctional (meth) acrylates, such as (meth) acrylate and ditrimethylolpropane hexa (meth) acrylate, ) And those having a hydroxyl group in acrylates, polyfunctional (meth) acrylate having a hydroxyl group partially modified with an alkyl group and ε- caprolactone hydroxyl groups of these alcohols, and the like.

Among the above-mentioned (meth) acrylate compounds (D) having at least one hydroxyl group, 2-hydroxyethyl (meth) acrylate is particularly preferred from the viewpoint of excellent curability and flexibility. From the viewpoint of easy workability, the polymerizable compound (G) described later in the present invention may be added during the reaction.

  In the second reaction of the present invention, the intermediates obtained after the first reaction are charged in an equivalence relationship such that the isocyanate groups are eliminated. Specifically, preferably, the OH group of the (meth) acrylate compound (D) having at least one or more hydroxyl group is 1.0 to 3.0 mol based on 1.0 mol of the NCO group of the intermediate obtained after the first reaction. 0 mol, more preferably 1.0 to 2.0 mol.

The second reaction of the present invention can also be performed without a solvent, but the viscosity of the product is high and the polymerizable compound (G) described later in the present invention and / or the present invention is used for improving workability. It is preferred to carry out under a mixture of The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is confirmed by a decrease in the amount of isocyanate. The catalyst described above may be added for the purpose of shortening the reaction time.
Here, it is preferable to carry out the reaction under mixing with a polymerizable compound (G) described later. When the compound is used as a diluent, the curable resin component occupies most of the compound, so that a problem hardly occurs at the time of curing, and a bad physical property does not easily occur. From the viewpoint of compatibility, it is preferable to use an alkyl (meth) acrylate or an alkylene (meth) acrylate (hereinafter, G-5) in combination.
Among them, compounds having a (meth) acryloyloxy group having a long chain of C4 to C34, more preferably C8 to C24, such as alkyl (meth) acrylate or alkylene (meth) acrylate, are preferable. By having such a structure, it is possible to obtain a product having excellent compatibility and transparency.

  Usually, a polymerization inhibitor such as 4-methoxyphenol has already been added to the acrylate compound used as a raw material, but a polymerization inhibitor may be added again during the reaction. Examples of such polymerization inhibitors include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-cresol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, phenothiazine and the like. The amount used is 0.01 to 1% by weight based on the reaction raw material mixture.

（上記式（Ａ）において、Ｂは水添ポリブタジエンポリオール化合物の水酸基を除いた骨格を表す。）

（上記式（Ｂ）において、Ｐは（Ｄ）成分のポリオール化合物の水酸基を除いた骨格を表す。）

（上記式（Ｃ）において、Ｒは水素原子又はメチル基を表す。）

（上記式（Ｄ）において、Ｄは脂環骨格を有するアルキレン鎖を表す。） The polyurethane compound (F) of the present invention thus obtained is obtained by reacting the hydroxyl group of the compound (A) with the isocyanate group or the hydroxyl group of the compound (B) obtained by the first reaction with the isocyanate group. The reacted residue (optionally, the residue in which the hydroxyl group of the compound (E) has reacted with the isocyanate group) and the compound having a terminal isocyanate group in which the residue in which the isocyanate group of the compound (C) has reacted with the hydroxyl group are bonded. It has a structure in which a residue where the terminal isocyanate group has reacted with the hydroxyl group of the compound (D) and a residue where the hydroxyl group of the compound (D) has reacted with the terminal isocyanate group are bonded via a urethane bond.
That is, as a specific example, a polyurethane compound having a structure in which the following formulas (A) to (D) are bonded via a reactive residue of the compound (B) is obtained.

(In the above formula (A), B represents a skeleton excluding a hydroxyl group of the hydrogenated polybutadiene polyol compound.)

(In the above formula (B), P represents a skeleton excluding the hydroxyl group of the polyol compound of the component (D).)

(In the above formula (C), R represents a hydrogen atom or a methyl group.)

(In the above formula (D), D represents an alkylene chain having an alicyclic skeleton.)

  The photosensitive resin composition of the present invention can contain the polyurethane compound (F) of the present invention and a polymerizable compound (G) other than the component (F) as optional components. Specific examples of the polymerizable compound (G) that can be used include a compound having a (meth) acryloyloxy group, a maleimide compound, a (meth) acrylamide compound, and an unsaturated polyester.

Specific examples of the compound having a (meth) acryloyloxy group that can be used in combination with the photosensitive resin composition of the present invention include (poly) ester (meth) acrylate (G-1); urethane (meth) acrylate (G-2) Epoxy (meth) acrylate (G-3); (poly) ether (meth) acrylate (G-4); alkyl (meth) acrylate or alkylene (meth) acrylate (G-5); A) acrylate (G-6); (meth) acrylate (G-7) having an alicyclic structure, and the like, but are not limited thereto.
The reactants can be obtained under known reaction conditions.

  The (poly) ester (meth) acrylate (G-1) that can be used in combination with the photosensitive resin composition of the present invention is a general term for (meth) acrylate having one or more ester bonds in the main chain, and is urethane (meth). Acrylate (G-2) is a general term for (meth) acrylates having at least one urethane bond in the main chain, and epoxy (meth) acrylate (G-3) is a monofunctional or higher epoxy compound and (meth) acrylate. As a general term for (meth) acrylate obtained by reacting acrylic acid, (poly) ether (meth) acrylate (G-4) is a general term for (meth) acrylate having one or more ether bonds in the main chain. Alkyl (meth) acrylate or alkylene (meth) acrylate (G-5) means that the main chain is straight-chain alkyl, branched alkyl, straight-chain or halogen at the terminal. (Meth) acrylate having an aromatic ring (G-6) is a general term for (meth) acrylates which may have a hydroxyl group and / or a (meth) acrylate having an aromatic ring in a main chain or a side chain. Is a (meth) acrylate having an alicyclic structure (G-7) having an alicyclic structure which may contain an oxygen atom or a nitrogen atom in a structural unit in a main chain or a side chain. It is used as a generic term for acrylate.

  Examples of the (poly) ester (meth) acrylate (G-1) that can be used in combination with the photosensitive resin composition of the present invention include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalate. Monofunctional (poly) ester (meth) acrylates such as acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, and caprolactone-modified tetrahydrofurfuryl (meth) acrylate; hydroxypivalic acid ester neopentyl glycol di (meth) Acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate; trimethylolpropane or glycerol 1 mole or more ε- caprolactone, .gamma.-butyrolactone, .delta.-valerolactone of triol obtained by adding a cyclic lactone compound of mono-, di- or tri (meth) acrylate;

Mono-, di-, tri- or tetra (meth) acrylate of tetraol obtained by adding one or more moles of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mole of pentaerythritol or ditrimethylolpropane A mono- or poly (meth) acrylate of hexaol obtained by adding 1 mol or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone to 1 mol of dipentaerythritol;

Diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, hexanediol and maleic acid, fumaric acid, succinic acid Acids, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, polybasic acids such as 5-sodium sulfoisophthalic acid, and their reaction products with anhydrides (Meth) acrylates of polyester polyols, such as (meth) acrylates of cyclic lactone-modified polyester diols comprising the diol component, polybasic acids and their anhydrides and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. Polyfunctional (poly) ester ( Can be mentioned data) acrylate, and the like, but is not limited thereto.

  The urethane (meth) acrylate (G-2) that can be used in combination with the photosensitive resin composition of the present invention includes a hydroxy compound (G-2-i) having at least one (meth) acryloyloxy group and an isocyanate compound (G- (B) is a general term for (meth) acrylates obtained by the reaction with

  Specific examples of the hydroxy compound (G-2-i) having at least one (meth) acryloyloxy group include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 4-hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy (Meth) acrylate compounds having various hydroxyl groups such as -3-phenoxypropyl (meth) acrylate, and a ring-opening reaction product of the above-mentioned (meth) acrylate compounds having a hydroxyl group and ε-caprolactone Etc. can be mentioned.

  Specific examples of the isocyanate compound (G-2-b) include, for example, P-phenylene diisocyanate, m-phenylene diisocyanate, P-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene isocyanate Aromatic diisocyanates such as diisocyanate, 4,4'-diphenylmethane diisocyanate and naphthalene diisocyanate; aliphatics such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate Or diisocyanates having an alicyclic structure; one or more burettes of the isocyanate monomer or the above-mentioned diisocyanate Things a trimer polyisocyanates of the isocyanate and the like; the and the isocyanate compound include polyisocyanates obtained by urethane reaction of the polyol compound.

When a urethane (meth) acrylate is obtained, a polyol is optionally reacted in the reaction between the hydroxy compound (G-2-i) having a (meth) acryloyloxy group and the isocyanate compound (G-2-lo). No problem.
Examples of the polyol that can be used include those having 1 to 10 carbon atoms such as neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Triols such as alkylene glycol, trimethylolpropane and pentaerythritol; alcohols having a cyclic skeleton such as tricyclodecanedimethylol and bis- [hydroxymethyl] -cyclohexane; and polyhydric alcohols and polybasic acids (for example, succinic acid) Phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc.), a polyester polyol obtained by the reaction of a polyhydric alcohol with ε-caprolactone. Lactone alcohol, polycarbonate polyol (for example, polycarbonate diol obtained by reaction of 1,6-hexanediol with diphenyl carbonate) or polyether polyol (for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-modified bisphenol A, etc.) And the like.

  The epoxy (meth) acrylate (G-3) that can be used in combination with the photosensitive resin composition of the present invention is obtained by reacting an epoxy resin having an epoxy group having one or more functionalities with (meth) acrylic acid (meth). ) A generic term for acrylate. Specific examples of the epoxy resin used as a raw material of the epoxy (meth) acrylate include phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, and resorcinol diglycidyl ether; bisphenol-A type epoxy resin and bisphenol-F type epoxy Resin, bisphenol-S type epoxy resin, bisphenol type epoxy compound such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound; hydrogenated bisphenol- A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexa Epoxy of Fluoropropane Hydrogenated bisphenol type epoxy compounds such as compounds; halogenated bisphenol type epoxy compounds such as brominated bisphenol-A type epoxy resin and brominated bisphenol-F type epoxy resin; alicyclic diglycidyl such as cyclohexanedimethanol diglycidyl ether compound Ether compounds; aliphatic diglycidyl ether compounds such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether; polysulfide-type diglycidyl ether compounds such as polysulfide diglycidyl ether; phenol Novolak epoxy resin, cresol novolak epoxy resin, trishydroxyphenylmethane epoxy resin, dicyclopentadiene phenol Epoxy resins, biphenol type epoxy resin, bisphenol -A novolac epoxy resins, naphthalene skeleton-containing epoxy resin, a heterocyclic epoxy resin or the like.

  Examples of the (poly) ether (meth) acrylate (G-4) that can be used in combination with the photosensitive resin composition of the present invention include, for example, butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, epichlorohydrin-modified butyl ( Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, etc. Functional (poly) ether (meth) acrylates;

  Alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate; ethylene oxide and propylene oxide Polyhydric hydroxyl compounds such as copolymers, copolymers of propylene glycol and tetrahydrofuran, hydrocarbon polyols such as polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, and (meth) acrylic Polyfunctional (meth) acrylates derived from acids; 1 mol or more of neopentyl glycol such as ethylene oxide, propylene oxide, butylene oxide, etc. Di (meth) acrylate of a diol obtained by adding Jo ether;

  Di (meth) acrylates of alkylene oxide modified bisphenols such as bisphenol A, bisphenol F and bisphenol S; alkylene oxide modified dialkylated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S (Meth) acrylate; mono-, di- or tri (meth) acrylate of triol obtained by adding one or more moles of a cyclic ether compound such as ethylene oxide, propylene oxide or butylene oxide to 1 mole of trimethylolpropane or glycerin;

  Mono, di, tri or tetra (meth) acrylate of triol in which 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide or butylene oxide is added to 1 mol of pentaerythritol or ditrimethylolpropane; 1 mol per 1 mol of dipentaerythritol Examples include polyfunctional (poly) ether (meth) acrylates such as triol to hexafunctional (meth) acrylate of hexaol to which a cyclic ether compound such as ethylene oxide, propylene oxide, and butylene oxide is added in an amount of at least mole.

  Examples of the alkyl (meth) acrylate or alkylene (meth) acrylate (G-5) that can be used in combination with the photosensitive resin composition of the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , N-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate , Isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acryle G, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, etc. Monofunctional (meth) acrylates;

  Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2 Di (meth) acrylates of hydrocarbon diols of -methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate;

Mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane (hereinafter, “poly” is used as a generic term for polyfunctional such as di, tri, tetra, etc.) and mono (meth) of glycerin Triols, tetraols, hexals such as acrylate or poly (meth) acrylate, pentaerythritol mono or poly (meth) acrylate, ditrimethylolpropane mono or poly (meth) acrylate, dipentaerythritol mono or poly (meth) acrylate Mono- or poly (meth) acrylates of polyhydric alcohols such as all;

Hydroxy group-containing (meth) acryls such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; and the like.

  Examples of the (meth) acrylate (G-6) having an aromatic ring that can be used in combination with the photosensitive resin composition of the present invention include monofunctional (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate. Di (meth) acrylates such as bisphenol A di (meth) acrylate and bisphenol F di (meth) acrylate; and the like, but not limited thereto.

  Examples of the (meth) acrylate (G-7) having an alicyclic structure that can be used in combination with the photosensitive resin composition of the present invention include, for example, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, Monofunctional (meth) acrylates having an alicyclic structure such as cyclopentenyl (meth) acrylate; di (meth) acrylates of hydrogenated bisphenols such as hydrogenated bisphenol A and hydrogenated bisphenol F; tricyclodecane dimethylol di ( Polyfunctional (meth) acrylates having a cyclic structure such as (meth) acrylate; alicyclic (meth) acrylates having an oxygen atom or the like in the structure such as tetrafurfuryl (meth) acrylate; However, the present invention is not limited to these.

  Examples of the compound having a (meth) acryloyl group that can be used in combination with the photosensitive resin composition of the present invention include, in addition to the compounds described above, for example, a reaction product of a (meth) acrylic acid polymer and glycidyl (meth) acrylate. Or a poly (meth) acrylic polymer (meth) acrylate such as a reaction product of a glycidyl (meth) acrylate polymer and (meth) acrylic acid; a (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate; Isocyanuric (meth) acrylates such as (meth) acryloxyethyl isocyanurate; (meth) acrylates having a polysiloxane skeleton; polybutadiene (meth) acrylate, melamine (meth) acrylate, and the like can also be used.

  Examples of the maleimide group-containing compound (G-8) that can be used in combination with the photosensitive resin composition of the present invention include, for example, Nn-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethylcarbonate, Monofunctional aliphatic maleimides such as maleimidoethyl-propyl carbonate, N-ethyl- (2-maleimidoethyl) carbamate; alicyclic monofunctional maleimides such as N-cyclohexylmaleimide; N, N-hexamethylenebismaleimide, polypropylene Aliphatic bismaleimides such as glycol-bis (3-maleimidopropyl) ether and bis (2-maleimidoethyl) carbonate; alicyclics such as 1,4-dimaleimidocyclohexane and isophoronebisurethanebis (N-ethylmaleimide) Bismaleimide; Maleimide acetic acid and PO A maleimide compound obtained by esterifying tetramethylene glycol, a carboxymaleimide derivative such as a maleimide compound obtained by esterifying maleimidocaproic acid with a tetraethylene oxide adduct of pentaerythritol, and various (poly) ols. (Poly) ester (poly) maleimide compounds and the like, but are not limited thereto.

  Examples of the (meth) acrylamide compound (G-9) that can be used in combination with the photosensitive resin composition of the present invention include monofunctional (meth) acrylamides such as acryloylmorpholine and N-isopropyl (meth) acrylamide; Examples thereof include polyfunctional (meth) acrylamides such as (meth) acrylamide.

  Examples of the unsaturated polyester (G-10) that can be used in combination with the photosensitive resin composition of the present invention include fumaric esters such as dimethyl malate and diethyl malate; and polyunsaturated esters such as maleic acid and fumaric acid. An esterification reaction product of a carboxylic acid and a polyhydric alcohol can be exemplified.

As the polymerizable compound (G) that can be used in combination with the photosensitive resin composition of the present invention, alkyl (meth) acrylate or alkylene (meth) acrylate (G-5) having low viscosity and excellent light resistance and workability can be used in combination. Preferably, the compound is not limited to the above-mentioned compounds, and any compound having one or more kinds of compounds having copolymerizability with the component (F) can be used in combination without particular limitation.
Among them, compounds having a (meth) acryloyloxy group having a long chain of C4 to C34, more preferably C8 to C24, such as alkyl (meth) acrylate or alkylene (meth) acrylate, are preferable. By having such a structure, a photosensitive resin composition having excellent compatibility and transparency can be obtained.

  In the photosensitive resin composition of the present invention, the proportion of the components (F) and (G) is not particularly limited, but the component (G) is added in an amount of 10 to 2,000 weight% with respect to 100% by weight of the component (F). %, Preferably from 20 to 1000% by weight.

  Specific examples of the photopolymerization initiator (H) used in the photosensitive resin composition of the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyclohexyl phenyl ketone, 2-methyl-1- [4 Acetophenones such as-(methylthio) phenyl] -2-morpholinopropan-1-one; anthraquino such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide; Benzophenones such as 4,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. . The proportion of these is usually 0.01 to 30% by weight, preferably 0.1 to 25% by weight, when the solid content of the photosensitive resin composition is 100% by weight.

  These can be used alone or as a mixture of two or more kinds. Further, tertiary amines such as triethanolamine and methyldiethanolamine, ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate are used. Can be used in combination with an accelerator such as a benzoic acid derivative. The amount of these accelerators to be added is 100% by weight or less based on the photopolymerization initiator (H), if necessary.

  Furthermore, the photosensitive resin composition of the present invention may contain a non-reactive compound, an inorganic filler, an organic filler, a silane coupling agent, a tackifier, a defoaming agent, a leveling agent, a plasticizer, Inhibitors, ultraviolet absorbers, flame retardants, pigments, dyes, and the like can be appropriately used.

  Specific examples of the non-reactive compound include liquid or solid oligomers and resins having low or no reactivity, such as alkyl (meth) acrylate copolymer, epoxy resin, liquid polybutadiene, Cyclopentadiene derivatives, saturated polyester oligomers, xylene resins, polyurethane polymers, ketone resins, diallyl phthalate polymers (dap resins), petroleum resins, rosin resins, fluorine-based oligomers, silicon-based oligomers, phthalate esters, phosphate esters, Glycol esters, citrate esters, aliphatic dibasic acid esters, fatty acid esters, epoxy plasticizers, castor oils, terpene hydrogenated resins polyisoprene skeleton, oligomers or polymers having a polybutadiene skeleton or xylene skeleton, and That es Le product, homopolymer, epoxy-modified polybutadiene, butadiene - styrene random copolymer, polybutene, and the like can be mentioned softening agents etc., but is not limited thereto. The weight ratio of such components in the ultraviolet-curable resin composition is usually 10 to 80% by weight, preferably 10 to 70% by weight.

  Examples of the inorganic filler include silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, and glass. , Mica, barium sulfate, alumina white, zeolite, silica balloon, glass balloon, and the like. These inorganic fillers may be added to and reacted with a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, or the like, to form a halogen group, an epoxy group, a hydroxyl group, a thiol group, or the like. It can also have a functional group.

  As the organic filler, for example, benzoguanamine resin, silicone resin, low-density polyethylene, high-density polyethylene, polyolefin resin, ethylene-acrylic acid copolymer, polystyrene, acrylic copolymer, polymethyl methacrylate resin, fluororesin, Nylon 12, nylon 6/66, phenolic resin, epoxy resin, urethane resin, polyimide resin and the like can be mentioned.

  Examples of the silane coupling agent include silane coupling agents such as γ-glycidoxypropyltremethoxysilane and γ-chloropropyltrimethoxysilane, and tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) ) Phosphite titanates, titanate coupling agents such as bis (dioctyl pyrophosphate) ethylene titanate; aluminum coupling agents such as acetoalkoxyaluminum diisopropylate; zirconium coupling agents such as acetylacetone / zirconium complex; be able to.

  Tackifiers, defoamers, leveling agents, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, pigments and dyes that can be used in the photosensitive resin composition of the present invention can be any known and commonly used ones. These can also be used without any particular limitation as long as the curability and resin properties are not impaired.

In order to obtain the photosensitive resin composition of the present invention, the components described above may be mixed, and the order and method of mixing are not particularly limited.
When various additives are present in the composition, the weight ratio of the various additives in the photocurable transparent adhesive composition is 0.01 to 3% by weight, preferably 0.01 to 1% by weight, more preferably Is 0.02 to 0.5% by weight.

  Although the photosensitive resin composition of the present invention does not substantially require a solvent, for example, ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetates such as ethyl acetate and butyl acetate, benzene, toluene, xylene and the like It is also possible to dilute the photosensitive resin composition of the present invention with other commonly used organic solvents such as aromatic hydrocarbons.

  The photosensitive resin composition of the present invention can be polymerized by irradiating ultraviolet light or visible light having a wavelength of 180 to 500 nm. In addition, it can be cured by irradiation with energy rays other than ultraviolet rays or by heat.

  As a light source of ultraviolet or visible light having a wavelength of 180 to 500 nm, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, and a short circuit Arc lamps, helium / cadmium lasers, argon lasers, excimer lasers, and sunlight can be mentioned.

  The photosensitive resin composition of the present invention has excellent adhesiveness to the substrate, excellent flexibility, weather resistance, high light resistance, and in addition to optical applications in which transparency needs to be maintained, ink, plastic paint, paper printing, It is useful in various fields such as metal coating, furniture coating, lining and adhesives, and in the electronics field such as insulating varnishes, insulating sheets, laminates, printed circuit boards, resist inks, and semiconductor encapsulants. . More specific applications include planographic printing inks, flexographic inks, gravure inks, ink fields such as screen inks, varnish fields, paper coating fields, woodwork coating fields, beverage can coating or printing ink fields, Flexible packaging film coating agent, printing ink or adhesive, thermal paper, thermal film coating agent, printing ink, adhesive, adhesive or optical fiber coating agent, liquid crystal display device, organic EL display device, touch panel image display device It is useful for applications such as air gap fillers for display devices (fillers for gaps between display devices and surface plates).

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

Synthesis Example 1
In a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller, GI-1000 manufactured by Nippon Soda Co., Ltd. (iodine value: 10.5, hydroxyl value: 69.2 mg · KOH) was used as a hydrogenated polybutadiene polyol compound. / G), 81.84 g (0.50 mol), 98.15 g (0.50 mol) of TCD alcohol DM (tricyclodecane dimethanol) manufactured by Celanese as a diol compound having an alicyclic skeleton, and Shin-Nakamura Chemical as a polymerizable compound 523.80 g of S-1800A (isostearyl acrylate) and 0.61 g of 4-methoxyphenol as a polymerization inhibitor were added, and the mixture was stirred until it became uniform, and the internal temperature was set to 50 ° C. Subsequently, 266.76 g (1.20 mol) of isophorone diisocyanate was added as a polyisocyanate compound and reacted at 80 ° C. until the target NCO content was reached. Next, 46.45 g (0.40 mol) of 2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. as a (meth) acrylate compound having at least one or more hydroxyl groups, and tin octylate as a urethanization reaction catalyst at 0. .37 g was added and reacted at 80 ° C., and when the NCO content became 0.1% or less, the reaction was terminated, thereby obtaining a polyurethane compound (F-1).

Synthesis Example 2
In a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller, GI-1000 manufactured by Nippon Soda Co., Ltd. (iodine value: 10.5, hydroxyl value: 69.2 mg · KOH) was used as a hydrogenated polybutadiene polyol compound. / G), 81.84 g (0.50 mol), 78.52 g (0.40 mol) of TCD alcohol DM (tricyclodecane dimethanol) manufactured by Celanese as a diol compound having an alicyclic skeleton, and Asahi Glass Co., Ltd. as a polyol compound. 101.10 g (0.10 mol) of Exenol 1020 (polypropylene glycol, hydroxyl value: 111 mg · KOH / g) manufactured by 558.71 g of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. as a polymerizable compound; 0.65 g of 4-methoxyphenol was added as a polymerization inhibitor. It was stirred until, and the internal temperature of 50 ° C.. Subsequently, 266.76 g (1.20 mol) of isophorone diisocyanate was added as a polyisocyanate compound and reacted at 80 ° C. until the target NCO content was reached. Next, 46.45 g (0.40 mol) of 2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. as a (meth) acrylate compound having at least one or more hydroxyl groups, and tin octylate as a urethanization reaction catalyst at 0. .39 g was added and reacted at 80 ° C., and when the NCO content became 0.1% or less, the reaction was taken as the end point to obtain a polyurethane compound (F-2).

Synthesis Example 3
In a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller, GI-1000 manufactured by Nippon Soda Co., Ltd. (iodine value: 10.5, hydroxyl value: 69.2 mg · KOH) was used as a hydrogenated polybutadiene polyol compound. / G) of 973.01 g (0.60 mol), 58.89 g (0.30 mol) of TCD alcohol DM (tricyclodecane dimethanol) manufactured by Celanese as a diol compound having an alicyclic skeleton, and Asahi Glass Co., Ltd. as a polyol compound. 101.10 g (0.10 mol) of Exenol 1020 (polypropylene glycol, hydroxyl value: 111 mg.KOH / g) manufactured by Shinen-Nakamura Chemical Co., Ltd., 61.80 g of S-1800A (isostearyl acrylate) as a polymerizable compound, 0.72 g of 4-methoxyphenol was added as a polymerization inhibitor, and It was stirred until, and the internal temperature of 50 ° C.. Subsequently, 266.76 g (1.20 mol) of isophorone diisocyanate was added as a polyisocyanate compound and reacted at 80 ° C. until the target NCO content was reached. Next, 46.45 g (0.40 mol) of 2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. as a (meth) acrylate compound having at least one or more hydroxyl groups, and tin octylate as a urethanization reaction catalyst at 0. .43 g was added and reacted at 80 ° C., and when the NCO content became 0.1% or less, the reaction was taken as the end point to obtain a polyurethane compound (F-3).

Comparative Synthesis Example 1
In a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller, GI-1000 manufactured by Nippon Soda Co., Ltd. (iodine value: 10.5, hydroxyl value: 69.2 mg · KOH) was used as a hydrogenated polybutadiene polyol compound. / G) as 810.84 g (0.50 mol), as a polyol compound, 505.50 g (0.50 mol) as Exenol 1020 (polypropylene glycol, hydroxyl value: 111 mg · KOH / g) manufactured by Asahi Glass Co., Ltd., and as a polymerizable compound. 698.37 g of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. and 0.81 g of 4-methoxyphenol as a polymerization inhibitor were added, and the mixture was stirred until uniform, and the internal temperature was set to 50 ° C. Subsequently, 266.76 g (1.20 mol) of isophorone diisocyanate was added as a polyisocyanate compound and reacted at 80 ° C. until the target NCO content was reached. Next, 46.45 g (0.40 mol) of 2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd. as a (meth) acrylate compound having at least one or more hydroxyl groups, and tin octylate as a urethanization reaction catalyst at 0. .49 g was added and reacted at 80 ° C., and when the NCO content became 0.1% or less, the reaction was terminated, thereby obtaining a polyurethane compound (U-1).

Formulation Example 1
20 parts by mass of the polyurethane compound (F-1) of Synthesis Example 1, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Blenmer LA (lauryl acrylate) manufactured by NOF Corporation, 18 parts by mass of Clearon M-105 (aromatic modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, GI-2000 manufactured by Nippon Soda Co., Ltd. 20 parts by mass of (1,2-hydrogenated polybutadiene glycol), 3 parts by mass of 4-HBA (4-hydroxybutyl acrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd., and Speed Cure TPO (2,4,6-trimethyl manufactured by LAMBSON) 0.5 parts by mass of benzoyldiphenylphosphine oxide, IRGACURE 184 (1-hydroxycyclobutane) manufactured by BASF (Hexyl phenyl ketone) 0.5 parts by mass was heated to 70 ° C. and mixed to obtain a resin composition of the present invention. The viscosity of this resin composition was 3500 mPa · s.

Formulation Example 2
20 parts by mass of the polyurethane compound (F-2) of Synthesis Example 2, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Blenmer LA (lauryl acrylate) manufactured by NOF Corporation, 18 parts by mass of Clearon M-105 (aromatic modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, GI-2000 manufactured by Nippon Soda Co., Ltd. 20 parts by mass of (1,2-hydrogenated polybutadiene glycol), 3 parts by mass of 4-HBA (4-hydroxybutyl acrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd., and Speed Cure TPO (2,4,6-trimethyl manufactured by LAMBSON) 0.5 parts by mass of benzoyldiphenylphosphine oxide, IRGACURE 184 (1-hydroxycyclobutane) manufactured by BASF (Hexyl phenyl ketone) 0.5 parts by mass was heated to 70 ° C. and mixed to obtain a resin composition of the present invention. The viscosity of this resin composition was 3600 mPa · s.

Formulation Example 3
20 parts by mass of the polyurethane compound (F-3) of Synthesis Example 3, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., 10 parts by mass of Blenmer LA (lauryl acrylate) manufactured by NOF Corporation, 18 parts by mass of Clearon M-105 (aromatic modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, GI-2000 manufactured by Nippon Soda Co., Ltd. 20 parts by mass of (1,2-hydrogenated polybutadiene glycol), 3 parts by mass of 4-HBA (4-hydroxybutyl acrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd., and Speed Cure TPO (2,4,6-trimethyl manufactured by LAMBSON) 0.5 parts by mass of benzoyldiphenylphosphine oxide, IRGACURE 184 (1-hydroxycyclobutane) manufactured by BASF (Hexyl phenyl ketone) 0.5 parts by mass was heated to 70 ° C. and mixed to obtain a resin composition of the present invention. The viscosity of this resin composition was 3700 mPa · s.

Comparative Formulation Example 1
20 parts by mass of the polyurethane compound (U-1) of Comparative Synthesis Example 1, 19 parts by mass of S-1800A (isostearyl acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., and 10 parts by mass of Blenmer LA (lauryl acrylate) manufactured by NOF Corporation 18 parts by mass of Clearon M-105 (aromatic modified hydrogenated terpene resin) manufactured by Yashara Chemical Co., Ltd., 10 parts by mass of LV-100 (polybutene) manufactured by JX Nippon Oil & Energy Corporation, GI- manufactured by Nippon Soda Co., Ltd. 2000 (1,2-hydrogenated polybutadiene glycol) 20 parts by mass, Osaka Organic Chemical Industry Co., Ltd. 4-HBA (4-hydroxybutyl acrylate) 3 parts by mass, LAMBSON speed cure TPO (2,4,6- 0.5 parts by mass of trimethylbenzoyldiphenylphosphine oxide, IRGACURE 184 (1-hydroxysiloxane) manufactured by BASF 0.5 parts by mass of (clohexyl phenyl ketone) was heated to 70 ° C. and mixed to obtain a resin composition of the present invention. The viscosity of this resin composition was 3,800 mPa · s.

Formulation Examples 1 to 3 and Comparative Formulation Example 1 are shown in Table 1, and the following evaluations were performed.

(Viscosity) The viscosity was measured at 25 ° C using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.).

  (Refractive index) The refractive index (25 ° C.) of the resin was measured with an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).

(Curing Shrinkage Ratio) Two 1 mm-thick slide glasses coated with a fluorine-based release agent were prepared, and one of the release agent-coated surfaces was coated with the obtained ultraviolet-curable resin composition to a thickness of 200 μm. It applied so that it might become. Thereafter, the two slide glasses were stuck together such that their release agent-coated surfaces faced each other. The resin composition was irradiated with ultraviolet rays having an integrated light amount of 3000 mJ / cm ^{2 through} a glass with a high-pressure mercury lamp (80 W / cm, ozone-less) to cure the resin composition. Thereafter, the two slide glasses were peeled off to prepare a cured product for measuring the specific gravity of the film. The specific gravity (DS) of the cured product was measured according to JIS K7112B method. Further, the liquid specific gravity (DL) of the resin composition was measured at 25 ° C. From the measurement results of DS and DL, the cure shrinkage was calculated from the following equation.
Curing shrinkage (%) = (DS-DL) ÷ DS × 100

(Rigidity) Two release-treated PET films were prepared, and one of the release surfaces was coated with the obtained ultraviolet-curable resin composition so as to have a thickness of 200 μm. Thereafter, the two PET films were bonded together such that the release surfaces faced each other. The resin composition was irradiated with ultraviolet rays having an integrated light amount of 3000 mJ / cm ^{2 through} a PET film with a high-pressure mercury lamp (80 W / cm, ozone-less) to cure the resin composition. Thereafter, the two PET films were peeled off to prepare a cured product for measuring the rigidity. The rigidity was measured by ARES (manufactured by TA Instruments).

(Transmittance) Two slide glasses having a thickness of 1 mm were prepared, and one of the slide glasses was coated with the obtained ultraviolet curable resin composition so that the cured film thickness became 200 μm. Thereafter, two slide glasses were bonded. The resin composition was cured by irradiating ultraviolet rays with a cumulative light amount of 3000 mJ / cm ^{2 through} a glass with a high-pressure mercury lamp (80 W / cm, ozone-less) to prepare a cured product for transmittance measurement. About the transparency of the obtained hardened | cured material, the transmittance | permeability in the wavelength region of 400-800 nm and 400-450 nm was measured using the spectrophotometer (U-3310, Hitachi High-Technologies Corporation). As a result, the transmittance at 400 to 800 nm was 90% or more, and the transmittance at 400 to 450 nm was 90% or more.

(Heat and moisture resistant adhesiveness) Prepare a 1 mm thick slide glass and a 1 mm thick glass plate, or a 1 mm thick glass plate with a polarizing film stuck on one side, and obtain an ultraviolet curable resin composition obtained on one side. Was applied so that the film thickness became 200 μm, and the other was bonded to the applied surface. The resin composition was irradiated with ultraviolet light having an integrated light amount of 3000 mJ / cm ^{2 through} a glass with a high-pressure mercury lamp (80 W / cm, ozone-less), and the resin composition was cured to prepare an adhesive evaluation sample. Using this, a heat resistance test at 85 ° C. and a humidity resistance test at 60 ° C. and 90% RH were performed and left for 100 hours. In the evaluation sample, peeling of the cured resin from the glass or polarizing film was visually confirmed, and the adhesion was evaluated according to the following evaluation criteria.
◎ ・ ・ ・ No peeling ○ ・ ・ ・ Slight peeling is seen like unevenness △ ・ ・ ・ Partially peeled off × ・ ・ ・ Peeled off

The photosensitive resin composition containing the polyurethane compound of the present invention is excellent in adhesiveness and flexibility, high in weather resistance and light resistance, and excellent in transparency, so that it is useful as an optical member application. Further, the cured product of the photosensitive resin composition of the present invention is useful as an adhesive for bonding a transparent display substrate.

Claims (13)

A reaction product of the compound (A) and the compound (B), the compound (C) and the compound (D) shown below, wherein the reaction ratio between the compound (A) and the compound (B) is 9.9 in molar ratio. : Polyurethane compound (F) having a ratio of 0.1 to 1: 1 .
Compound (A): hydrogenated polybutadiene polyol compound Compound (B): diol compound having an alicyclic skeleton
Compound (C): aliphatic diisocyanate compound or aromatic di- isocyanate compound compound (D): at least one or more hydroxyl groups (meth) acrylate compound A reaction product of the compound (A) and the compound (B), the compound (C), the compound (D) and the compound (E) shown below, wherein the reaction ratio between the compound (A) and the compound (B) is molar. Polyurethane compound (F) having a ratio of 9.9: 0.1 to 1: 1 .
Compound (A): hydrogenated polybutadiene polyol compound Compound (B): diol compound having an alicyclic skeleton
Compound (C): aliphatic diisocyanate compound or aromatic di- isocyanate compound compound (D): at least one or more hydroxyl groups (meth) acrylate compound
Compound (E): a polyol compound other than compound (A) and compound (B) The polyurethane compound (F) according to claim 2, wherein the iodine value of the hydrogenated polybutadiene polyol compound (A) is 20 or less. The polyurethane compound (F) according to any one of claims 1 to 3, wherein the diol compound (B) having an alicyclic skeleton is a diol compound having an alicyclic structure having 20 or less carbon atoms. The polyurethane compound (F) according to any one of claims 1 to 4, wherein the diol compound (B) having an alicyclic skeleton is tricyclodecanedimethanol. The polyurethane compound (F) according to any one of claims 1 to 5, wherein the polyisocyanate compound (C) is an aliphatic diisocyanate compound. The polyurethane compound (F) according to any one of claims 1 to 6, wherein the (meth) acrylate compound (D) having at least one or more hydroxyl groups is 2-hydroxyethyl (meth) acrylate. A photosensitive resin composition comprising the polyurethane compound (F) according to any one of claims 1 to 7 and a polymerizable compound (G) other than (F). The photosensitive resin composition according to claim 8, wherein the polymerizable compound (G) is an alkyl (meth) acrylate or an alkylene (meth) acrylate. The photosensitive resin composition according to claim 8, further comprising a photopolymerization initiator (H). A cured product of the photosensitive resin composition according to any one of claims 8 to 10. Compound or fillers photosensitive resin composition for a gap between the display device and the surface plate comprising the resin composition according to any one of claims 1 to 1 0. A touch panel comprising a cured product layer of the filler according to claim 12.