CN101171278B

CN101171278B - Photosensitive resin compositions, cured articles of the compositions, and films containing the compositions

Info

Publication number: CN101171278B
Application number: CN2006800158019A
Authority: CN
Inventors: 龟谷英照; 今澄贵公男; 狩野浩和; 小柳敬夫; 水谷刚; 德田清久; 小林大祐; 内藤正弘
Original assignee: Nippon Kayaku Co Ltd
Current assignee: Nippon Kayaku Co Ltd
Priority date: 2005-05-12
Filing date: 2006-04-25
Publication date: 2011-01-19
Anticipated expiration: 2026-04-25
Also published as: JP5209310B2; TW200707093A; WO2006120887A1; CN101171278A; JPWO2006120887A1; TWI382998B; KR20080005412A; KR101299025B1

Abstract

To provide a photosensitive resin composition suitable for hard coats which permits thick coating with low curling and little causes crack, and to provide a resin composition for the protective coating for high-density optical discs which is excellent in transparency and the resistance to water absorption and which exhibits high endurance with little warpage, and cured articles of the composition. [MEANS FOR SOLVING PROBLEMS] A photosensitive resin obtained by reacting an isocyanate compound (A) prepared by reacting a diisocyanate compound (a) with an alcohol compound (b) having at least two hydroxyl groups in the molecule or an isocyanate compound (A') derived from a diisocyanate compound (a) by converting either of the isocyanate groups into an isocyanurate ring structure with a mixture (B) of polyfunctional (meth)acrylate compounds, namely, polyhydric alcohol (meth)acrylates, which mixture comprises a polyhydric alcohol (meth)acrylate having one or more hydroxyl groups and a polyhydric alcohol (meth)acrylate wherein all the hydroxyl groups are esterified.

Description

Photosensitive resin composition, its solidify material and the film that contains this material

Technical field

The present invention relates to photosensitive resin composition and solidified coating thereof (solidify material), described composition is used to form the solidified coating (solidify material) with high breaking point stress and excellent wear.The invention still further relates to the film with described solidified coating, this film has improved the surface hardness of plastics such as polyester, acrylic acid or the like (acryl), polycarbonate, polyethersulfone etc., and is difficult for taking place by curling that cure shrinkage causes.The invention still further relates to the high density compact disc of future generation that uses described resin combination and solidify material, have low water-absorbent especially and low shrinkability when solidifying, and the good transparency and weather resistance.

Background technology

At present, plastics are widely used in the industrial circle that comprises automotive industry, consumer electronics industry and Electrical and Electronic industry.A large amount of reasons of using plastics except plastics reasons such as easily processing and the transparency be good, are that also plastics have in light weight, character such as price is low, good optical characteristics.Yet the shortcoming of plastics is softer than glass etc., and its surface is easy to scratch.

In order to improve these shortcomings of plastics, traditional method is normally coated on the surface of plastics and is increased hard coating agent.These are operational to increase hard coating agent and can enumerate: the thermoset of silicone, acrylate or melamine increases hard coating agent.Wherein, because silicone increases the excellent specific property that hard coating agent has high rigidity, therefore be widely used.Silicone increases hard coating agent and is used to most of high added value goods, as eyeglass and lens.Yet it is long that silicone increases the set time that hard coating agent needs, and price is expensive, so the hard coating agent that increases that their are used as continuous film processed is not to be preferred.Increase in the hard coating agent though attempted that the antireflection filler is joined silicone, because described to increase hard coating agent be heat reactive resin, solidifying of described filler can be implemented by heating.As a result, also there is not a kind of silicone that does not damage the low reflection of the transparency to increase hard coating agent at present.

Recently, developed the hard coating agent that increases of radiation curing esters of acrylic acid.Because the hard coating agent that increases of radiation curing is to make it to solidify to form immediately hard film by being exposed in the radiation (activation-energy-ray) such as UV-light, therefore the speed of handling is very fast.In addition, goods have excellent character, as hardness and wear resistance, thereby cause total cost to descend, and the result can prevail in the hard coat field.Radiation curing increase the continuous processing that hard coating agent is particularly preferred for following film: polyester film, polyacrylic acid ester film, esters of acrylic acid film, polycarbonate film, vinyl chloride film, tri acetyl cellulose film, polyethersulfone film etc.Polyester film is widely used in the anti-scatter film of glass or the photomask of automobile, such as the film of using on contact type panel, liquid-crystal display, the CRT panel TV set electronic materials such as (CRT monitor), perhaps be used for improving ornamental laminated film on the steel plate such as the casing of the household electrical appliance of refrigerator etc., or be used for the film on white board surface.In all these are used, all need hard coating, so that its surface is not scratched.

Recently, have in its surface and be coated with the indicating meter (as CRT monitor and liquid-crystal display) that increases hard coating agent film there are the following problems: because the film surface smooth planar causes because reflection makes display screen be difficult for seeing, and causes visual fatigue.Therefore, can prevent the hard coat processing of surface reflection in some cases according to its purposes needs.In order to prevent surface reflection, proposed a kind of method that prevents surface reflection, comprising: on film, be coated with the resin of the radiation curing of the filler that is dispersed with mineral filler or organic fine particles, thereby form ununiformity (AG processing) on the surface; The another kind of method of proposing comprises: the order according to high refractor and forming low-refractive-index layer on film provides a multilayered structure, thereby prevents shielding and reflection (AR processing) by the difference of refractive index; Another method of proposing is with the combination (AG/AR processing) of above-mentioned two kinds of methods etc.

Along with to having the needs of functional hard coat, carried out big quantity research at present, with the hardness of further raising hard coat itself.For example, in JP2001-113648A, disclosed: improve hardness by in resin combination, adding multifunctional ammonia ester acrylate.Yet, take place to curl because a large amount of contractions of employed multifunctional ammonia ester acrylate when solidifying are easy to cause cracking and film, so the add-on of its composition has to be restricted.

Usually the example of actual used optical record medium comprises: CD (high density compact disc), MD (magneto-optic disk), CD-R (CD-R storer), CD-RW (writing optical disk storer again) etc.They are by forming recording layer film and reflectance coating on the thick polycarbonate substrate of 1.2mm, and it is not subjected to the protective layer of external factors interferential ultraviolet curing coating agent constructed to form protection.In addition, recently, reality can be used DVD-R, DVD-RW, DVD-RAM, DVD+R, DVD+RW etc., result: the double refraction problem that has solved polycarbonate substrate, and make the diameter of laser spots littler by producing the polycarbonate substrate that thickness is 0.6mm (be traditional substrate thickness half), and with two kinds of substrate combinations, with further raising recording density.All these CDs all be by with above-mentioned identical mode, on the 0.6mm polycarbonate substrate, form recording layer film and reflectance coating, and has formed protect and the protective layer or the bonding coat of the ultraviolet hardening of bonding purpose constructed.

Yet the DVD recording medium still is in the state of recording capacity shortage as the recording medium of addressing large storage capacity in the time limit of service of its digital broadcasting.(JP11-273147A) proposed following such CD: thick recording layer and the transparent layer of lamination 100 μ m on substrate, and by from transparent covering layer rather than from the blue laser-light write and the read data of POLYCARBONATE SHEET, this is in fact as high density compact disc of future generation.

About forming tectal method, a kind of method is to be the transparent film of 100 μ m in conjunction with thickness, and another kind of method is by using ultraviolet curable resin to form the thick one deck of 100 μ m on recording layer.In order to form ultraviolet curable resin layer, the method for proposing to adopt the 2P method and using spin coater.The example that is used to form the ultraviolet curing agent on recording sheet is the 2P agent, for example the described composition of JP5-059139A and JP5-132534A.In addition, the protection coating agent is proposed, for example described in JP3-131605A, JP3-172358A and the JP2003-268263A.

Summary of the invention

Solve related problems with the present invention

Develop the higher hard coat of hardness under the condition that is restricted for thickness at basement membrane, though adopted various measures, comprise: use itself thickness as the relatively large film of material, raising degree of crosslinking, the setting of hard, but increase the result of degree of crosslinking and film thickness, the problem that can produce cracking and curl and so on.

The objective of the invention is to, a kind of resin combination and solidified coating and the film with this solidified coating of activation energy radial curing is provided, described composition can make the curling little of thick film coating, and is suitable for producing the hard coat that can not crack.Another object of the present invention provides a kind of resin combination of low cure shrinkage, and said composition is applicable to the transparent coating of the high density compact disc that does not almost have warpage and excellent in te pins of durability.

Solve the method for related problems

The present inventor broad research the approach that achieves the above object, found to have the photosensitive resin composition of specific composition, thereby finished the present invention.

Specifically, the present invention relates to following:

(1) photosensitive resin, the reaction by following component obtains:

Isocyanate compound (A) is the reaction product that the alkylol cpd (b) of at least two hydroxyls is arranged in diisocyanate cpd (a) and its molecule; Or isocyanate compound (A '), derived from diisocyanate cpd (a), wherein any forms isocyanuric acid ester ring structure in two isocyanate groups;

Multifunctional (methyl) acrylic compound, mixture (B) as (methyl) acrylic compound of polyvalent alcohol comprising: have all multifunctional (methyl) acrylic compound of esterification of multifunctional (methyl) acrylic compound of one or more hydroxyls and wherein all hydroxyl;

(2) according to the photosensitive resin of above (1), wherein, the weight-average molecular weight that has the alkylol cpd (b) of at least two hydroxyls in its molecule is 100～1500;

(3) according to the photosensitive resin of above (1) or (2), wherein, multifunctional (methyl) acrylic compound with one or more hydroxyls is three (methyl) vinylformic acid pentaerythritol ester and/or five (methyl) vinylformic acid dipentaerythritol ester;

(4) according to above (1) any one photosensitive resin in (3), wherein, mixture (B) is the mixture of pentaerythritol triacrylate and pentaerythritol tetracrylate;

(5) a kind of photosensitive resin composition, it comprises as any one described photosensitive resin and Photoepolymerizationinitiater initiater (C) in above (1) to (4);

(6) according to the photosensitive resin composition of above (5), it comprises polymerisable compound (D);

(7) according to the photosensitive resin composition of above (6), wherein, polymerisable compound (D) is to be selected from one or more following compounds: (gathering) ester (methyl) acrylate (D-1), ammonia ester (methyl) acrylate (D-2), epoxy (methyl) acrylate (D-3), (gathering) ether (methyl) acrylate (D-4), (methyl) alkyl acrylate or (methyl) vinylformic acid alkylene ester (D-5), (methyl) acrylate (D-6) with aromatic ring, (methyl) acrylate (D-7) with alicyclic structure, compound with maleimide base group, (methyl) acrylamide compound and unsaturated polyester;

(8) solidify material of any one described photosensitive resin composition in above (5) to (7);

(9) a kind of film, it comprises the solidify material described in above (8);

(10) according to above (5) any one photosensitive resin composition in (7), it is the protection coating agent that is used for CD;

(11) according to the solidify material of the photosensitive resin composition of above (8), wherein, the water-intake rate of the solidify material that records in the time of 25 ℃ is≤2.0%, and the shrinking percentage when solidifying is≤6%;

(12) according to the solidify material of above (8) or (11), wherein, blue laser is that transmissivity in the solidify material of 50～150 μ m is 〉=70% at film thickness.

(13) a kind of CD, it has the solidify material of one deck according to above (8), (11) or (12); And

(14) according to the CD of above (13), wherein, curing material layer is structured on incident one side of described video disc recording light and/or playback light.

The advantage of invention

The solidified coating of photosensitive resin composition of the present invention (solidify material) has low curling, and crackle takes place hardly, can also improve the hardness of solidified coating.Coating can be applicable to each field that needs high rigidity except hard coat film, promptly, printing ink, plastic coating, paper printing, metallic coating, such as each coatings art, lining, tackiness agent and the electronic applications of furniture coating, as insullac, insulcrete, laminated wood, printed circuit board (PCB), etching resisting ink, encapsulating semiconductor glue etc.

In addition; resin combination of the present invention and solidify material thereof can provide the protection coating agent; and the solidify material that is used for high density compact disc; this CD has excellent transparency and low water absorbable; and demonstrate the high-durability that does not almost have warpage; therefore, they are very useful using blue laser to read and/or write in the used CD.

Preferred forms of the present invention

Photosensitive resin of the present invention is by being made by isocyanic ester compound (A) or isocyanic ester compound (A ') mixture (B) reaction with multifunctional (methyl) acrylic compound, wherein, isocyanate compound (A) is the reaction product of diisocyanate cpd (a) and the alkylol cpd (b) that at least two hydroxyls are arranged in its molecule; Isocyanate compound (A ') is derived from diisocyanate cpd (a), and wherein any forms isocyanuric acid ester ring structure in two isocyanate groups; Multifunctional (methyl) acrylic compound comprises all multifunctional (methyl) acrylic compound of esterification of multifunctional (methyl) acrylic compound with one or more hydroxyls and wherein all hydroxyl as the mixture (B) of (methyl) acrylic compound of polyvalent alcohol.

Example according to diisocyanate cpd of the present invention (a) has: wherein two isocyanate groups are at the substituted compound of line style stable hydrocarbon, cyclic saturated hydrocarbon or aromatic hydrocarbon.Their object lesson includes but not limited to: line style stable hydrocarbon vulcabond, tetramethylene diisocyanate, 1 for example, hexamethylene-diisocyanate, 2,2,4-trimethylammonium-hexamethylene diisocyanate or 2,4,4-trimethylammonium-hexamethylene diisocyanate, two isocyanic acids 1,12-12 methylene esters, lysinediisocyanate etc.; Cyclic saturated hydrocarbon vulcabond, for example isophorone two isocyanide esters, dicyclohexyl methane diisocyanate, methylene-bis (isocyanic acid 4-cyclohexyl), hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tolylene diisocyanate, norbornylene vulcabond etc.; And aromatic diisocyanate, for example, 2,4 toluene diisocyanate, 1,3-Xylene Diisocyanate, PPDI, 6-sec.-propyl-1,3-phenylene diisocyanate, 1,5-naphthalene diisocyanate etc.Above-claimed cpd can and use separately or uses with two or more mixture.

The alkylol cpd (b) that at least two alkyl are arranged in the molecule is not specifically limited, but preferable weight-average molecular weight is 100～1500 compound.Object lesson comprises: polyether polyol class, polytetramethylene glycol (polybutylene glycol), poly-1 for example, 4-butyleneglycol (polytetramethylene glycol), polypropylene glycol, polyoxyethylene glycol etc.; The polyester polyol class, for example polyethylene glycol adipate, poly-hexanodioic acid-1,4-butanediol ester, polycaprolactone etc.; Glycols, for example ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, neopentyl glycol etc.; The alicyclic ring alcohols, for example, hexanaphthene dimethyl alcohol (cyclohexanedimethlol), Hydrogenated Bisphenol A, A Hydrogenated Bisphenol A F, the alcohols that comprises the spiral skeleton, tristane dimethyl alcohol, pentacyclopentadecandimethanol dimethyl alcohol etc. or its alkylene oxides; Chain alkyl glycols side chain or straight chain, for example hydrogenated butadiene polymer etc.; Bisphenols, for example dihydroxyphenyl propane, Bisphenol F etc.; The oxirane affixture of bisphenols; Polyalcohols, for example TriMethylolPropane(TMP), two (trishydroxymethyl) propane, tetramethylolmethane, Dipentaerythritol etc.; And the oxirane affixture of these polyalcohols; React the polyester polyols alcohols that makes by these polyalcohols and polyprotonic acid (as hexanodioic acid); And polycarbonate polyol class.

With having the reaction of the alkylol cpd (b) of at least two hydroxyls to produce the isocyanate compound (A) that is used to prepare photosensitive resin of the present invention in diisocyanate cpd (a) and the molecule, this reaction is to have the feeding manner of a kind of like this equivalent relation of remaining isocyanate groups to carry out after making reaction.When the inlet amount of alkylol cpd (b) reduces and charge ratio when increasing, almost can not be retained in the isocyanate compound (A) of generation result, the increase of photosensitive resin generation rimose tendency by alkylol cpd deutero-material.In addition, when feed rate ratio descended, molecular weight increased, and tended to influence the curing properties of photosensitive resin composition.

Specifically, the OH group can be made as in the alkylol cpd (b), with respect to the NCO group in the 1.0mol isocyanate compound (a), is 0.1～0.9mol, preferred 0.20～0.85mol.

Though reaction can be carried out under condition of no solvent,, in order to improve operability, reaction can be carried out in solvent when product viscosity is higher.The object lesson of solvent for use is: ketone, for example acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.; Aromatic hydrocarbons, for example benzene,toluene,xylene, tetramethyl-benzene etc.; Ethylene glycol bisthioglycolate ethers, for example glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dme, dipropylene glycol diethyl ether, triglyme, triglycol diethyl ether etc.; Ester class, for example ethyl acetate, butylacetate, methylcellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, Ethyl carbitol acetate ester, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetic ester, pentanedioic acid dialkyl (for example Methyl glutarate etc.), succinic acid dialkyl ester (for example dimethyl succinate); Cyclic ester class, for example gamma-butyrolactone; And petroleum solvent class, for example sherwood oil, petroleum naphtha, hydrogenated naphtha, solvent naphtha etc.In addition, also can use the mixture of these solvents.

Temperature of reaction is usually 30～150 ℃ of scopes, preferred 50～100 ℃ of scopes.

For example, by IR (infrared absorption spectrum) method or by using the back titration of acid, behind remaining isocyanic ester and excessive alkali reaction, when the amount minimizing of isocyanic ester, the terminal point that can be defined as reacting.

For shortening the reaction times, can add catalyzer, basic catalyst or an acidic catalyst all can use.

The example of basic catalyst is: amine, for example pyridine, pyrroles, triethylamine, diethylamine, dibutylamine, ammonium etc.; And phosphine class, for example tributylphosphine, triphenylphosphine etc.

The example of an acidic catalyst is a lewis acid catalyst, for example copper naphthenate, cobalt naphthenate, zinc naphthenate, aluminium butoxide, titanium tetraisopropylate, four butanols zirconiums, aluminum chloride, 2 ethyl hexanoic acid tin, three lauric acid tin octylates, dibutyl tin dilaurate, oxalic acid tin octylate etc.When adding catalyzer, be that 100 weight parts are benchmark in the isocyanate compound (A) that is produced, the catalyzer add-on is generally 0.1～1 weight part.

Preparing the used isocyanate compound of photosensitive resin of the present invention (A ') is the compound with isocyanuric acid ester ring structure, and this compound is by utilizing a formed trimer of isocyanate groups in above-mentioned diisocyanate cpd (a).Specifically, the trimer that can mention is tolylene diisocyanate, hexamethylene diisocyanate and Trimerization of Isophorone Diisocyanate thing.

To prepare used multifunctional (methyl) acrylic compound with one or more hydroxyls (as (methyl) acrylic compound of polyvalent alcohol) of photosensitive resin of the present invention and wherein all hydroxyl all esterified multifunctional (methyl) acrylic compound mixture (B) be not particularly limited.Their object lesson is: the mixture of (methyl) vinylformic acid pentaerythritol ester and four (methyl) vinylformic acid pentaerythritol ester; The mixture of one or more multifunctional (methyl) acrylate and six (methyl) vinylformic acid dipentaerythritol ester, described multifunctional (methyl) acrylate is selected from: five (methyl) vinylformic acid dipentaerythritol ester, four (methyl) vinylformic acid dipentaerythritol ester, three (methyl) vinylformic acid dipentaerythritol ester and two (methyl) vinylformic acid dipentaerythritol ester; And the mixture of TriMethylolPropane(TMP) two (methyl) acrylate and trimethylolpropane tris (methyl) acrylate.And, can multiplely be used in combination in these mixtures.

The example of mixture (B) preferably includes: contain the mixture of three (methyl) vinylformic acid pentaerythritol ester and/or five (methyl) vinylformic acid dipentaerythritol ester, the mixture of preferred especially pentaerythritol triacrylate and pentaerythritol tetracrylate.The ratio that has multifunctional (methyl) acrylic compound of one or more hydroxyls in mixture (B) is to comprise wherein 20～95 weight % of mixture (B) total amount of all hydroxyls all esterified multifunctional (methyl) acrylic compound.

About the mixture (B) that is used to prepare photosensitive resin of the present invention, (methyl) acrylic compound as polyvalent alcohol, comprise following compound: have multifunctional (methyl) acrylic compound of one or more hydroxyls and wherein all hydroxyl all esterified multifunctional (methyl) acrylic compound, can use by polyvalent alcohol and carry out (methyl) reaction product that acroleic acid esterification obtained.

In addition, following polymerizable compound (D) can add wherein for using.

Photosensitive resin of the present invention can make by above-mentioned isocyanate compound (A) or isocyanate compound (the A ') mixture reaction with multifunctional (methyl) acrylic compound, and this reaction is not have the feeding manner of the so a kind of equivalent relation of remaining isocyanate groups to carry out after making reaction.Specifically, the mixture charging of multifunctional (methyl) acrylic compound, preferably with respect to the NCO group in the 1.0mol isocyanate compound, the OH group is 1.0～3.0mol, more preferably 1.0～2.0mol.

Though reaction can be carried out under condition of no solvent, but also can in solvent, carry out, perhaps can be undertaken by adding polymerizable compound described below (D), perhaps can also in polymerizable compound (D), carry out, described solvent based be similar to the alkylol cpd (b) that in above-mentioned diisocyanate cpd (a) and molecule, has at least two hydroxyls react in used solvent.

For example, by IR (infrared absorption spectrum) method or by using the back titration of acid, behind remaining isocyanic ester and excessive alkali reaction, when the amount minimizing of isocyanic ester, can be defined as reaction end.

For shortening the reaction times, can add the compound that is similar to the catalyzer in alkylol cpd (b) reaction that has at least two hydroxyls in above-mentioned diisocyanate cpd (a) and its molecule, this compound amount is identical with above-mentioned catalyst levels.

To the mixture (B) of above-mentioned multifunctional (methyl) acrylic compound, normally add initiators for polymerization, for example p methoxy phenol earlier.Yet, between this reaction period, can add as quinhydrones, p methoxy phenol, 2,4 dimethyl 6 tert butyl phenol, 3-hydroxythiophenol, para benzoquinone, 2, the initiators for polymerization of 5-dihydroxyl-para benzoquinone, thiodiphenylamine etc.When adding initiators for polymerization, be benchmark with the mixture (B) of multifunctional (methyl) acrylic compound, its add-on is 0.01～1 weight %.In addition, be 100 weight % when being benchmark with the solid content in the photosensitive resin composition, the photosensitive resin content in the photosensitive resin composition of the present invention is generally 5～90 weight %, is preferably 10～86 weight %.

Photosensitive resin composition of the present invention can contain light polymerization initiator (C).Example to light polymerization initiator (c) does not limit, and can enumerate particularly: bitter almond oil camphor class, for example bitter almond oil camphor, benzoin methylether, ethoxybenzoin, bitter almond oil camphor propyl ether, bitter almond oil camphor ethyl isobutyl ether etc.; The phenyl methyl ketone class, phenyl methyl ketone, 2 for example, 2-diethoxy-phenyl acetophenone, 1,1-Er Lvyixianben, 2-hydroxy-2-methyl-phenyl-1-acetone, diethoxy phenyl methyl ketone, 1-hydroxy-cyclohexyl benzophenone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone etc.; The anthraquinone class, for example, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone etc.; The thioxanthene ketone, for example 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone, 2-clopenthixal ketone etc.; Ketal class, for example phenyl methyl ketone dimethyl ketal, benzyl dimethyl ketal etc.; The benzoquinones class, for example benzoquinones, 4-benzoyl-4 '-methyldiphenyl base sulphur, 4,4 '-dimethylamino benzoquinones etc.; Phosphinoxides, for example, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide etc.When being made as 100 weight % with the solid content in the photosensitive resin composition, the additional proportion of these Photoepolymerizationinitiater initiaters (C) is generally 0.01～30 weight %, preferred 0.1～25 weight %.

These Photoepolymerizationinitiater initiaters (C) can use separately, and perhaps two or more is used in combination, but also can be used in combination with reaction promotor, described reaction promotor for example, tertiary amines is as triethylamine, methyldiethanolamine etc.; Benzoic acid derivative, N for example, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isopentyl ester etc.When using these reaction promotors, its add-on is≤100 weight % with respect to Photoepolymerizationinitiater initiater (C).

Photosensitive resin compound of the present invention also can contain polymerizable compound (D).The example of these polymerizable compounds (D) has: have the compound of (methyl) acryloyl-oxy group, the compound with maleimide base group, (methyl) acrylamide compound, unsaturated polyester etc.

Example with compound of (methyl) acryloyl-oxy group comprises: (gathering) ester (methyl) acrylate (D-1), carbamate (methyl) acrylate (D-2), epoxy type (methyl) acrylate (D-3), (gathering) ether (methyl) acrylate (D-4), (methyl) alkyl acrylate or (methyl) vinylformic acid alkylene ester (D-5), have aromatic ring (methyl) acrylate (D-6), have (methyl) Class C acid esters (D-7) of alicyclic structure etc.

Example with compound of maleimide base group comprises: simple function aliphatic series maleimide, for example N-normal-butyl maleimide, N-n-hexyl maleimide, 2-maleimide amino-ethyl ethyl-carbonate, 2-maleimide amino-ethyl-propyl carbonate, N-ethyl-(2-maleimide amino-ethyl)-carbamate etc.; The alicyclic maleimide of simple function, for example, N-cyclohexyl maleimide etc.; The aliphatic series bismaleimides, N for example, N-hexa-methylene bismaleimides, two (the 3-maleimide aminopropyl) ethers of polypropylene glycol, two (2-maleimide amino-ethyl) carbonic ether etc.; Alicyclic bismaleimide amine, for example, 1,4-dimaleimide hexanaphthene, isophorone double carbamate two (N-ethyl maleimide) etc.; (gathering) ester type (gathering) maleimide compound, produce by various (polynary) alcohol and the esterification of carboxyl maleimide derivatives, for example, by maleimide acetate and poly-1, the maleimide compound that the esterification of the affixture of the maleimide compound that the esterification of 4-butyleneglycol is produced, the Fourth Ring oxidative ethane (tetraethylene oxide) by maleimide caproic acid and tetramethylolmethane is produced etc.

The example of (methyl) acrylamide compound comprises: simple function (methyl) acrylic amide, for example acryloyl morpholine, N-sec.-propyl (methyl) acrylamide etc.; Multifunctional (methyl) acrylic amide, for example methylene-bis (methyl) acrylamide etc.

The example of unsaturated polyester is: fumarate, for example dimethyl fumarate, DEF etc.; And the esterification reaction product of multivalence unsaturated carboxylic acid (for example toxilic acid, fumaric acid etc.) and polyvalent alcohol.

(gathering) ester (methyl) acrylate (D-1) as the compound with (methyl) acryloxy, is the common name that has (methyl) acrylate of one or more ester bonds in its main chain.Their example comprises: simple function polyester type (methyl) esters of acrylic acid, for example (methyl) tetrahydrofurfuryl acrylate of (methyl) acrylate of the succsinic acid of (methyl) acrylate of the phthalic acid of (methyl) vinylformic acid of caprolactone modification-2-hydroxyl ethyl ester, oxyethane and/or epoxy pronane modification, oxyethane modification, caprolactone modification etc.; Two (methyl) acrylate of neopentyl glycol-hydroxy new pentane acid ester; Hydroxy new pentane acid ester neopentyl glycol two (methyl) acrylate of caprolactone modification etc.; Phthalic ester two (methyl) acrylate of Epicholorohydrin modification; The list of trivalent alcohol-, two-or three (methyl) acrylate, described trivalent alcohol is that the macrolide compounds (for example 6-caprolactone, gamma-butyrolactone, δ-Wu Neizhi etc.) by general-mole or many moles joins-makes in the TriMethylolPropane(TMP) of mole or the glycerine; The list of tetravalent alcohol-, two-, three-or four (methyl) acrylate, described tetravalent alcohol is that the macrolide compounds (for example 6-caprolactone, gamma-butyrolactone, δ-Wu Neizhi etc.) by general-mole or many moles joins in one mole tetramethylolmethane or the ditrimethylolpropane and makes; List (methyl) acrylate or poly-(methyl) acrylate of polyvalent alcohol (for example trivalent alcohol, tetravalent alcohol, pentavalent alcohol or oneself unit's alcohol), described polyvalent alcohol are to join in one mole the Dipentaerythritol by the macrolide compounds (for example 6-caprolactone, gamma-butyrolactone, δ-Wu Neizhi etc.) with a mole or many moles to make; (methyl) acrylate of polyester polyol, it is the product of diol component and polyprotonic acid reaction, described polyol component for example (gathers) ethylene glycol, (gathering) propylene glycol, (gathering) 1,4-butyleneglycol, (gathering) butyleneglycol, 3-methyl isophthalic acid, 5-pentanediol, hexylene glycol etc., described polyprotonic acid is toxilic acid, fumaric acid, succsinic acid, hexanodioic acid, phthalic acid, m-phthalic acid, hexahydro-phthalic acid, tetrahydrophthalic acid, dimeracid, sebacic acid, nonane diacid, 5-sulphur m-phthalic acid sodium etc. for example, or its acid anhydride; And multifunctional (gathering) ester type (methyl) acrylate, (methyl) acrylate of the polyester type dibasic alcohol of cyclic lactone modification for example, the polyester type dibasic alcohol of described cyclic lactone modification is formed by aforementioned diprotic acid, polyprotonic acid or its acid anhydride and 6-caprolactone, gamma-butyrolactone or δ-Wu Neizhi.

Carbamate (methyl) acrylate (D-2), as compound with (methyl) acryloxy, be the common name that has (methyl) acrylate of one or more amino-formate bonds in its main chain, and be to react (methyl) acrylic compound that makes by oxy-compound (D-2-A) and isocyanate compound (D-2-B) with at least one (methyl) acryloxy.

Example with oxy-compound (D-2-A) of at least one (methyl) acryloxy comprises: (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxyl ethyl ester, single (methyl) vinylformic acid cyclohexanedimethanoester ester, poly-single (methyl) vinylformic acid glycol ester, poly-single (methyl) vinylformic acid propylene glycol ester, three (methyl) vinylformic acid pentaerythritol ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, and this class has (methyl) the acrylate compound of hydroxyl and the ring-opening reaction product of 6-caprolactone.

The example of isocyanate compound (D-2-B) comprising: aromatic diisocyanate, for example PPDI, m-benzene diisocyanate, p-Xylol vulcabond, m xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4, '-'-diphenylmethane diisocyanate, naphthalene diisocyanate etc.; Aliphatic series or alicyclic structure vulcabond, isophorone diisocyanate, 1 for example, hexamethylene-diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, hydrogenated xylene diisocyanate, norbornylene vulcabond, lysinediisocyanate etc.; The burette-modified form of one or more isocyanate-monomers; Polyisocyanates, for example the trimeric isocyanuric acid ester of these diisocyanate cpds; Urethane by diisocyanate cpd and above-mentioned polyol compound reacts the polyisocyanate compounds that makes.

Reaction with oxy-compound (D-2-A) and isocyanate compound (D-2-B) of at least one (methyl) acrylamido, can according to above-mentioned isocyanate compound (A) or isocyanate compound (A ') and with the reacting phase of the mixture (B) of multifunctional (methyl) acrylic compound with mode carry out.

Epoxy type (methyl) acrylate (D-3) as the compound with (methyl) acryloxy, is the common name by compound (methyl) acrylic compound that reaction makes with (methyl) vinylformic acid that contains one or more epoxide groups.

The example that contains the compound of one or more epoxide groups comprises: phenyl diglycidyl ether class, for example, quinhydrones diglycidyl ether, pyrocatechol diglycidyl ether, Resorcinol diglycidyl ether etc.; The bisphenol epoxies compounds, for example bisphenol A epoxide resin, bisphenol F epoxy resin, bisphenol-s epoxy resin, 2, two (the 4-hydroxyphenyl)-1,1,1,3,3 of 2-, the epoxy compounds of 3-HFC-236fa etc.; A Hydrogenated Bisphenol A epoxy compounds class, hydrogenated bisphenol A epoxy resin for example, A Hydrogenated Bisphenol A F Resins, epoxy, A Hydrogenated Bisphenol A S Resins, epoxy, hydrogenation 2, two (the 4-hydroxyphenyl)-1,1,1,3,3 of 2-, the epoxy compounds of 3-HFC-236fa etc.; Halogenated bisphenol epoxy compounds, for example bromo bisphenol A epoxide resin, bromo bisphenol F epoxy resin, alicyclic diglycidyl ether compounds, for example cyclohexanedimethanol diglycidyl ether compound etc.; Aliphatic series diglycidyl ether compound, for example 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, glycol ether diglycidylether etc.; Many sulphur diglycidylether (polysulfidediglycidyl ether) compounds, for example many sulphur diglycidylether etc.; Phenol novolac epoxy resin, cresols novolac epoxy resin, three (hydroxyphenyl) methane epoxy ring grease, Dicyclopentadiene (DCPD) phenol epoxy resin, bisphenol epoxy, dihydroxyphenyl propane-novolac epoxy resin, the Resins, epoxy that contains the naphthalene skeleton, heterocyclic ring epoxy resins etc.

Epoxy type (methyl) acrylate (D-3) can make by the compound that contains one or more epoxy group(ing) is reacted under the popular response condition with (methyl) vinylformic acid.

(gathering) ether (methyl) acrylate (D-4) as the compound with (methyl) acryloyl-oxy group, is the common name that has (methyl) acrylate of one or more ehter bonds in its main chain.Their example comprises: simple function (gathering) ether type (methyl) esters of acrylic acid, for example (methyl) butyl acrylate of (methyl) vinylformic acid butoxy ethyl ester, (methyl) vinylformic acid butoxy triglycol ester, Epicholorohydrin modification, (methyl) vinylformic acid two cyclopentenes oxygen base ethyl esters, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid ethyl carbitol ester, (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid Nonylphenoxy macrogol ester etc.; Alkylene glycol two (methyl) esters of acrylic acid, for example poly-two (methyl) vinylformic acid glycol ester, poly-two (methyl) vinylformic acid propylene glycol ester, poly-two (methyl) vinylformic acid butanediol ester, poly-two (methyl) vinylformic acid 1,4-butanediol ester etc.; Multifunctional (methyl) esters of acrylic acid derived from (methyl) vinylformic acid and multivalence oxy-compound, described multivalence oxy-compound is multipolymer, the hydro carbons polyalcohols of multipolymer, propylene glycol and the tetrahydrofuran (THF) of oxyethane and propylene oxide for example, for example polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene diol and hydrogenated butadiene polymer glycol etc.; Two (methyl) acrylate of dibasic alcohol, in described dibasic alcohol, the cyclic ethers (for example epoxy second hexane, propylene oxide and butylene oxide ring) of a mole or many moles is joined-neopentyl glycol of mole in; Two (methyl) acrylate of the bisphenols of oxirane modification (for example dihydroxyphenyl propane, Bisphenol F, bisphenol S); Two (methyl) acrylate of the A Hydrogenated Bisphenol A class of oxirane modification (for example Hydrogenated Bisphenol A, A Hydrogenated Bisphenol A F, A Hydrogenated Bisphenol A S); The list of trivalent alcohol-, two-or three (methyl) acrylate, described trivalent alcohol makes by one mole or many moles of cyclic ether compounds (for example oxyethane, propylene oxide and butylene oxide ring) being joined in one mole TriMethylolPropane(TMP) or the glycerine; The list of trivalent alcohol-, two-or three (methyl) acrylate, in described trivalent alcohol ,-mole or many moles cyclic ether compounds (for example oxyethane, propylene oxide and butylene oxide ring) joined in one mole tetramethylolmethane or the ditrimethylolpropane make; Multifunctional (gathering) ether type (methyl) esters of acrylic acid, for example three-to (methyl) acrylate of six-functional hexanol, wherein, the cyclic ether compounds (for example oxyethane, propylene oxide and butylene oxide ring) of a mole or many moles is joined in one mole the Dipentaerythritol.

(methyl) alkyl acrylate or (methyl) vinylformic acid alkylene ester (D-5), as compound with (methyl) acryloxy, be (methyl) vinylformic acid straight chained alkyl ester, or the common name of (methyl) vinylformic acid branched alkyl ester, their all available halogen atoms and/or hydroxyl replace.Their example comprises: simple function (methyl) acrylate, for example (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate, (methyl) vinylformic acid dodecane ester etc.; Two (methyl) acrylate of hydro carbons dibasic alcohol, for example two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid propylene glycol ester, two (methyl) vinylformic acid 1,4-butanediol ester, two (methyl) vinylformic acid 1,6-hexylene glycol ester, two (methyl) vinylformic acid DOPCP, two (methyl) vinylformic acid 2-methyl isophthalic acid, 8-ethohexadiol ester, two (methyl) vinylformic acid 1,9-nonanediol ester, two (methyl) vinylformic acid decamethylene-glycol ester etc.; The list of polyvalent alcohol (for example trivalent alcohol, tetravalent alcohol and hexavalent alcohol)-or poly-(methyl) esters of acrylic acid, for example single (methyl) acrylate, two (methyl) acrylate or three (methyl) acrylate (be used as " gather " here multifunctional group (for example two-, three-, four-, etc.) general name), the list of list (methyl) acrylate of glycerine or poly-(methyl) acrylate, tetramethylolmethane-or the list of poly-(methyl) acrylate, ditrimethylolpropane-or the list of poly-(methyl) acrylate, Dipentaerythritol-or gather (methyl) acrylate; And (methyl) acrylate that contains hydroxyl, for example (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester etc.

(methyl) acrylate (D-6) with aromatic ring as the compound with (methyl) acryloxy, has the common name of aromatic ring (methyl) acrylate in its main chain or side chain.Their example comprises: simple function (methyl) acrylate, for example (methyl) phenyl acrylate, (methyl) vinylformic acid benzyl ester etc.; And two (methyl) acrylate, for example dihydroxyphenyl propane two (methyl) acrylate, Bisphenol F two (methyl) acrylate etc.

(methyl) acrylate (D-7) with alicyclic structure as the compound with (methyl) acryloxy, is to have the alicyclic structure that can contain Sauerstoffatom or nitrogen-atoms in its main chain or side chain (methyl) acrylic acid common name as component units.Their example comprises: have simple function (methyl) acrylate of alicyclic structure, for example (methyl) cyclohexyl acrylate, (methyl) vinylformic acid ring pentyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid two cyclopentenes esters etc.; Two (methyl) acrylate of A Hydrogenated Bisphenol A class (for example Hydrogenated Bisphenol A, A Hydrogenated Bisphenol A F etc.); Multifunctional (methyl) acrylate with alicyclic structure, for example two (methyl) vinylformic acid tristane dihydroxy methyl esters etc.; Alicyclic (methyl) acrylate that in structure, has Sauerstoffatom, for example four furfuryl groups (methyl) acrylate etc.

Except above-claimed cpd, the example that can be included in the polymerizable compound (D) in the photosensitive resin composition of the present invention has: poly-(methyl) acrylic acid based polymer (methyl) acrylate ((meth) acryl polymer (meth) acrylate), the for example reaction product of (methyl) acrylic ester polymer and (methyl) glycidyl acrylate, or (methyl) glycidyl acrylate polymkeric substance and (methyl) acrylic acid reaction product; Has amino (methyl) acrylate, for example (methyl) dimethylaminoethyl acrylate etc.; Isocyanuric acid ester type (methyl) acrylate, for example isocyanuric acid three (methyl) acryloxy ethyl ester etc.; (methyl) acrylate with polysiloxane skeleton; Poly-(methyl) vinylformic acid divinyl ester; Melamine (methyl) acrylate etc.In addition, also can use have can with the compound of the character of described photosensitive resin composition copolymerization, this compound is not particularly limited, and described photosensitive resin composition is to make by isocyanate compound (A) or isocyanate compound (A ') mixture (B) reaction with multifunctional (methyl) acrylic compound.

Be used for photosensitive resin composition of the present invention, be used for solidified polymerizable compound (D) after being dispersed on the film to preferably include following: the mixture of three (methyl) vinylformic acid pentaerythritol ester and pentaerythritol tetracrylate; The mixture of mixture, TriMethylolPropane(TMP) two (methyl) acrylate and trimethylolpropane tris (methyl) acrylate of five (methyl) vinylformic acid dipentaerythritol ester, four (methyl) vinylformic acid dipentaerythritol ester, three (methyl) vinylformic acid dipentaerythritol ester or two (methyl) vinylformic acid dipentaerythritol ester and six (methyl) vinylformic acid dipentaerythritol ester etc.

In photosensitive resin composition of the present invention; when photosensitive resin composition of the present invention is when being used as the protection coating agent of CD; the compound that is used for polymerizable compound (D) is preferred: two (methyl) vinylformic acid DOPCP; two (methyl) vinylformic acid tristane dihydroxy methyl esters; TriMethylolPropane(TMP) two (methyl) acrylate of hydroxy pivalin aldehyde modification; two (methyl) acrylate of neopentyl glycol-hydroxypivalic acid ester; poly-two (methyl) vinylformic acid glycol ester; two (methyl) vinylformic acid, two ring pentyl esters; two (methyl) vinylformic acid 1,6-hexylene glycol ester; poly-two (methyl) vinylformic acid propylene glycol ester; dihydroxyphenyl propane two (methyl) acrylate of oxyethane modification; the trimethylolpropane tris of epoxy hexane upgrading (methyl) acrylate; four (methyl) vinylformic acid pentaerythritol ester of oxyethane modification; three [(methyl) propylene acyloxy ethyl] isocyanuric acid ester etc.

When photosensitive resin composition of the present invention contains polymerizable compound (D), in the resin combination that obtains by isocyanic ester compound (A) or isocyanate compound (A ') and the reaction of multifunctional (methyl) acrylic compound is 100 weight %, polymerizable compound (D) content is preferably 10～2000 weight %, is preferably 50～1000 weight % especially.

Photosensitive resin composition of the present invention, according to service requirements, can suitably contain: anergy compound, mineral filler, organic filler, silane coupling agent, tackifier, defoamer, levelling agent, softening agent, antioxidant, UV light absorber, fire retardant, pigment, dyestuff etc.

The compound of anergy is the oligopolymer or the resin of the liquid or solid of low reactivity or anergy, for example (methyl) alkyl acrylate copolymer, Resins, epoxy, liquid polybutadiene, two pentamethylene diene derivatives, saturated polyester oligopolymer, xylene resin, polyether polyols with reduced unsaturation, ketone resin, Phthalic acid, diallyl ester polymkeric substance (DAP resin), petroleum resin, Gum Rosin, fluorine-containing oligomer, silicone oligopolymer etc.

The example of mineral filler comprises: silicon-dioxide, silicon oxide, lime carbonate, Calucium Silicate powder, magnesiumcarbonate, magnesium oxide, talcum, kaolin, clay, calcined clay, zinc oxide, zinc sulfate, aluminium hydroxide, aluminum oxide, glass, mica, barium sulfate, white lake, zeolite, silicon ball (silica ballon), glass sphere (glass ballon) etc.For these mineral fillers, by adding silane coupling agent, titanate coupling agent, aluminum coupling agent, zirconate coupling agent etc., and with the method for mineral filler reaction, thereby can give these mineral filler functional groups, for example halogen atom, epoxy group(ing), hydroxyl and thiol group.

The example of organic filler comprises: benzo guanamine resin, silicone resin, new LDPE (film grade), high density polyethylene(HDPE), polyolefin resin, ethylene/acrylic acid copolymer, polystyrene, acrylate copolymer, plexiglass, fluorocarbon resin, nylon 12, nylon 6/66, phenol resins, Resins, epoxy, urethane resin, polyimide resin etc.

Photosensitive resin composition of the present invention can contain the known and common employed tackifier of any routine, defoamer, levelling agent, softening agent, antioxidant, UV light absorber, fire retardant, pigment and dyestuff, also unrestricted to this, as long as their are without detriment to solidified nature and characteristic of photosensitive resin composition.

Photosensitive resin composition of the present invention can by will be above-mentioned each component make after mixing, there is no particular restriction as for blended order and method.

Though photosensitive resin composition of the present invention is to containing solvent and have no special requirements, but can use after with organic solvent diluting, described organic solvent can be enumerated: ketone, for example methyl ethyl ketone and methyl iso-butyl ketone (MIBK); Acetate esters, for example ethyl acetate and butylacetate; Aromatic hydrocarbons, for example benzene, toluene and dimethylbenzene; And other is generally used for dissolving the solvent of photosensitive resin composition.

The polymerization of photosensitive resin composition of the present invention can be by irradiation UV-light or the wavelength visible light at 180～500nm, that is, activation-energy-ray carries out, and these solidify material are also included within the present invention.

The example of the source of release of activation-energy-ray has: low pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, chemical lamp, black lamp, xenon-mercury lamp, Excimer lamp, short-arc lamp, He-Cd laser device, argon laser, excimer laser, daylight etc.

Photosensitive resin composition of the present invention can be used as coating agent, surface treatment agent, tackiness agent, plastic material, moulding material, laminating material, adherend, be used for following tackiness agent: printing ink, metal is aluminium, iron and copper for example, plastics, for example vinylchlorid, acrylic acid or the like, polycarbonate, polyethylene terephthalate, polyethylene, polypropylene etc., pottery, glass for example, timber, printer paper, and fiber.The film that contains the solidify material of photosensitive resin composition of the present invention is also included within the present invention.

Particularly, can be used for ink area, for example planography printing ink and trap printing-ink, flexographic ink, gravure printing ink, screen printing ink etc., the varnish field, field, paper coating agent is used for the coating material field of wood working, the coating material or the printing-ink that are used for beverages can, the coating agent that is used for flexible packaging film, printing-ink or adherend, building paper, the coating agent that is used for insulation film made, printing-ink, tackiness agent, adherend or coating optical fibers agent.

When resin combination of the present invention was used as the resin combination that CD uses, the viscosity that records 25 ℃ the time with B-type viscometer was preferably 100～5000mPaS.During curing the shrinking percentage of solidify material preferred≤6%, and its water-intake rate (in the time of 25 ℃, recording) preferred≤2.0%.

The method that the protection coating agent that use resin combination conduct of the present invention is used for CD is coated with is 50～100 μ m as long as make the thickness of film without limits.In fact adoptable coating process for example has, spin-coating method, 2P method, rolling method, silk screen print method etc.

Because use the blue laser of about 400nm to be used for reading and/or writing at high density compact disc of future generation, in the solidify material of film thickness 50～150 μ m the transmissivity of about 400～500nm be preferably 〉=70%.

In addition, in CD of the present invention, compact disk structure preferably makes the curing material layer of the resin combination of ultraviolet hardening be structured in the recording light of CD and/or the light incident side of playback light.

Embodiment

The present invention will be described more specifically by embodiment, and the present invention is not subjected to the restriction of the following example then.Molecular weight is a weight-average molecular weight, and adopts GPC (gel permeation chromatography) to record.

Embodiment 1

In the reactor that disposes reflux exchanger, agitator, thermometer and thermoswitch, add Takelac U-24 10T (Mitsui Takeda Chemicals Inc., hexanodioic acid 1, the 4-butanediol ester, hydroxyl value is 114.8mgKOH/g) (97.8g) isophorone diisocyanate (44.5g) (NCO:0.4mol equivalent) of (OH:0.2mol equivalent), and 80 ℃ of reactions down, till NCO content reaches theoretical value by the reaction with hydroxyl.Then, the inside reactor temperature is reduced to 50 ℃, then add 4-methoxyphenol (0.122g) as initiators for polymerization and dibutyl tin dilaurate (0.122g) as the urethane catalyst for reaction, and be stirred to and make it to mix.Mixture (101.0g) (OH:0.22mol equivalent) (ratio of mixture with pentaerythritol triacrylate and pentaerythritol tetracrylate, weight part: 65/35, hydroxyl equivalent: 458.9 equivalents) add with the feeding manner that is divided into three batches, purpose is to make internal temperature be no more than 70 ℃.After interpolation finishes, be reflected under 70 ℃ and proceed, when above-mentioned NCO content reach≤0.1% the time, be made as the terminal point of reaction.The viscosity of prepared photosensitive resin (C-1) is 33.1 PaS (E type viscometer, 60 ℃) and Mw=7400 (use gpc measurement, transform to polystyrene).

Embodiment 2

Disposing reflux exchanger, the reactor of agitator, thermometer and thermoswitch, add PTG-850 (Hodogaya Chemical Co., Ltd., gather 1, the 4-butyleneglycol, hydroxyl value 127.9mgKOH/g) (87.7g) (OH:0.2mol equivalent) and isophorone diisocyanate (44.5g) (NCO:0.4mol equivalent), and 80 ℃ of down reactions, by with the reaction of hydroxyl, till making NCO content reach theoretical value.Then, the inside reactor temperature is reduced to 50 ℃, then add 4-methoxyphenol (0.177g) as initiators for polymerization and dibutyl tin dilaurate (0.177g) as the urethane catalyst for reaction, and be stirred to and make it to mix.Mixture (101.1g) (OH:0.22mol equivalent) (ratio of mixture with pentaerythritol triacrylate and pentaerythritol tetracrylate, weight part: 65/35, hydroxyl equivalent: 458.9 equivalents) to be divided into three batches feeding manner adding, purpose is to make interior internal temperature be no more than 70 ℃.Behind reinforced finishing, be reflected under 70 ℃ and proceed, when above-mentioned NCO content reach≤0.1% the time, be made as the terminal point of reaction.The viscosity of prepared photosensitive resin (C-2) is 23.9PaS (E type viscometer, 60 ℃) and Mw=7800 (measure with GPC, transform to polystyrene).

Embodiment 3

In the reactor that disposes reflux exchanger, agitator, thermometer and thermoswitch, adding is in order to the diatomic alcohol compounds (30.4g) (OH:0.2mol equivalent) and the isophorone diisocyanate (44.5g) (NCO:0.4mol equivalent) of following formula (1) expression, and 90 ℃ of reactions down, by with the reaction of hydroxyl, till making NCO content reach theoretical value.Then, the inside reactor temperature is reduced to 50 ℃, then add 4-methoxyphenol (0.088g) as initiators for polymerization, dibutyl tin dilaurate (0.088g) as urethane catalyst for reaction and MEK (2-butanone) (44.0g) as reaction solvent, and be stirred to and make it to mix.Mixture (101.0g) (OH:0.22mol equivalent) (ratio of mixture with pentaerythritol triacrylate and pentaerythritol tetracrylate, weight part: 65/35, hydroxyl equivalent: 458.9 equivalents) add with the feeding manner that is divided into three batches, purpose is to make internal temperature be no more than 70 ℃.Behind reinforced finishing, be reflected under 70 ℃ and proceed, when above-mentioned NCO content reach≤0.1% the time, be set at reaction end.The viscosity of prepared photosensitive resin (C-3) is 14.0PaS (E type viscometer, 25 ℃) and Mw=3500 (measure with GPC, transform to polystyrene).

Embodiment 4

In the reactor that disposes reflux exchanger, agitator, thermometer and thermoswitch, adding is in order to the diatomic alcohol compounds (39.3g) (OH:0.4mol equivalent) and the isophorone diisocyanate (88.9g) (NCO:0.8mol equivalent) of following formula (2) expression, and 90 ℃ of reactions down, by with the reaction of hydroxyl, this reaction is performed until NCO content is reached till the theoretical value.Then, the inside reactor temperature is reduced to 50 ℃, then add 4-methoxyphenol (0.165g) as initiators for polymerization, dibutyl tin dilaurate (0.165g) as urethane catalyst for reaction and MEK (2-butanone) (82.5g) as reaction solvent, and be stirred to and make it to mix.Mixture (201.9g) (OH:0.44mol equivalent) (ratio of mixture with pentaerythritol triacrylate and pentaerythritol tetracrylate, weight part: 65/35, hydroxyl equivalent: 458.9 equivalents) add with the feeding manner that is divided into three batches, purpose is to make internal temperature be no more than 70 ℃.Behind reinforced finishing, be reflected under 70 ℃ and proceed, when above-mentioned NCO content reach≤0.1% the time, be set at reaction end: the viscosity of prepared photosensitive resin (C-4) is 5.8PaS (E type viscometer, 25 ℃) and Mw=2900 (measure with GPC, transform to polystyrene).

Embodiment 5

In the reactor that disposes reflux exchanger, agitator, thermometer and thermoswitch, adding is in order to the diatomic alcohol compounds (43.7g) (OH:0.4mol equivalent) and the isophorone diisocyanate (88.9g) (NCO:0.8mol equivalent) of following formula (3) expression, and 90 ℃ of reactions down, by with the reaction of hydroxyl, reaction is performed until NCO content is reached till the theoretical value.Then, the inside reactor temperature is reduced to 50 ℃, then add 4-methoxyphenol (0.167g) as initiators for polymerization, dibutyl tin dilaurate (0.167g) as urethane catalyst for reaction and MEK (2-butanone) (83.6g) as reaction solvent, and be stirred to and make it to mix.Mixture (201.9g) (OH:0.44mol equivalent) (ratio of mixture with pentaerythritol triacrylate and pentaerythritol tetracrylate, weight part: 65/35, hydroxyl equivalent: 458.9 equivalents) add with the feeding manner that is divided into three batches, purpose is to make internal temperature be no more than 70 ℃.Behind reinforced finishing, be reflected under 70 ℃ and proceed, when above-mentioned NCO content reach≤0.1% the time, be set at reaction end.The viscosity of prepared photosensitive resin (C-5) is 15.2PaS (E type viscometer, 25 ℃) and Mw=3000 (measure with GPC, transform to polystyrene).

Embodiment 6

In the reactor that disposes reflux exchanger, agitator, thermometer and thermoswitch, add 4-methoxyphenol (0.067g) as initiators for polymerization and dibutyl tin dilaurate (0.067g) as the urethane catalyst for reaction, and be stirred to and make it to mix.Add pentaerythritol triacrylate and pentaerythritol tetracrylate mixture (101.0g) (OH:0.22mol equivalent) (ratio of mixture, weight part: 65/35, hydroxyl equivalent: 458.9 equivalents), and the inside reactor temperature is made as 50 ℃.Then, (the hexamethylene diisocyanate trimer: a kind of compound that contains isocyanurate ring) (33.6g) (NCO:0.2mol equivalent) adds with the feeding manner that is divided into three batches, and purpose is to make internal temperature be no more than 70 ℃ with TPA-100.After charging finishes, be reflected under 70 ℃ and proceed, when above-mentioned NCO content reach≤0.1% the time; Be set at reaction end.The viscosity of the photosensitive resin that is obtained (C-6) is 12.6 PaS (E type viscometer, 60 ℃) and Mw=6200 (measure with GPC, transform to polystyrene).

Embodiment 7

In the reactor that disposes reflux exchanger, agitator, thermometer and thermoswitch, add 4-methoxyphenol (0.161g) as initiators for polymerization and dibutyl tin dilaurate (0.161g) as the urethane catalyst for reaction, and be stirred to and make it to mix.Add five vinylformic acid dipentaerythritol ester and six vinylformic acid dipentaerythritol ester mixture (288.5g) (OH:0.22mol equivalent) (ratio of mixture, weight part: 40/60, hydroxyl equivalent: the 1311.3g/ equivalent), and the inside reactor temperature is made as 50 ℃.(the hexamethylene diisocyanate trimer: a kind of compound that contains isocyanurate ring) (33.6g) (NCO:0.2mol equivalent) adds with the feeding manner that is divided into three batches, and purpose is to make internal temperature be no more than 70 ℃ with TPA-100 then.After charging finishes, be reflected under 70 ℃ and proceed, when above-mentioned NCO content reach≤0.1% the time; Be set at reaction end.The viscosity of the photosensitive resin that is obtained (C-7) is 36.0PaS (E type viscometer, 60 ℃) and Mw=11200 (measure with GPC, transform to polystyrene).

The contrast synthesis example

At the configuration reflux exchanger, agitator, in the reactor of thermometer and thermoswitch, mixture (101.1g) (OH:0.22mol the equivalent) (ratio of mixture that adds pentaerythritol triacrylate and pentaerythritol tetracrylate, weight part: 65/35, hydroxyl equivalent: 458.9 equivalents), 4-methoxyphenol (0.067g) as initiators for polymerization and dibutyl tin dilaurate (0.067g) as the urethane catalyst for reaction, and under 70 ℃, be stirred to and make it to mix, in 3 hours time period, be added dropwise to isophorone diisocyanate (17.8g) (NCO:0.16 molar equivalent) then.Behind reinforced finishing, be reflected under 70 ℃ and proceed, when above-mentioned NCO content reach≤0.1% the time, be set at reaction end, thereby make photosensitive resin (H-1).

Embodiment 8～13 and reference examples 1

To the photosensitive resin (C-3) that makes by embodiment 3 and embodiment 4 respectively and (C-4) distilling off solvent MEK in advance, thereby obtain independent resin Composition.Other resin does not deal with, and keeps its original state.Preparation resin combination as shown in the following Table 1.These resin combinations are coated on the rust steel plate with scraping strip coating machine, use seal strip (thickness: 200 μ m) make up sealing coat (wall) on stainless steel plate.With the ultraviolet ray of UV lamp irradiation, the UV lamp is 10cm apart from the height of stainless steel plate to resin combination on the plate in nitrogen atmosphere, and the stainless steel plate gait of march is 5m/min, thereby obtains to have the thick solidified coating of about 200 μ m.

Table 1

Content (g)	Embodiment						Reference examples
								(C-1) (C-2) (C-3) (C-4) (C-5) (C-6) (H-1)	8 80	9 80	10 80	11 80	12 80	13 80	1 80
HDDA ^1 Irg.184? ^2	20 5	20 5	20 5	20 5	20 5	20 5	20 5

^*1:HDDA; Nippon Kayaku Co., the product of Ltd., diacrylate 1,6-hexylene glycol ester

^*(2:Irg.184 Irgacure 184); The product of Ciba Specialty Chemicals, 1-hydroxyl-cyclohexyl-phenyl-ketone

Test case 1

The film that makes in embodiment 8～13 or the reference examples 1 is estimated by following items.The result is as shown in table 2.

(pencil hardness)

Use pencil cut machine to measure the pencil hardness of coated film according to JISK 5400.Particularly, pencil is arranged on the film to be tested with 45, and on the top, applies the 1kg load, this film is scratched about 5mm to determine cut.

(tension test)

Film is cut into 1.0cm * 4.0cm, use Tensilon (stretching testing machine) to measure following data.

1. Young's modulus

2. breaking point stress

3. breaking point elongation

Table 2: the result of the value of commenting

	Pencil hardness	Young's modulus (MPa)	Breaking point stress (MPa) Pa)	Breaking point elongation (%)
					Embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 13 reference examples 1	HB HB 4H 5H 4H 6H 6H	715 631 1260 1346 1246 1340 1070	33.7 27.8 23.3 28.8 22.7 34.4 17.8	8.1 6.9 2.8 3.5 3.4 4.1 2.0

The result of table 2 shows: use photosensitive resin composition of the present invention to make to stretch the film that can keep again simultaneously than high Young's modulus and high breaking point stress.

Resin combination on the plate is used the ultraviolet ray of UV lamp irradiation in nitrogen atmosphere,

Embodiment 14～19 and reference examples 2

To the photosensitive resin (C-3) that makes by embodiment 3 and embodiment 4 respectively and (C-4) distilling off solvent MEK in advance, thereby obtain independent resin Composition.Other resin does not deal with, and keeps its original state.Preparation resin combination as shown in the following Table 3.These resin combinations are coated on the polyester film that easily carried out adhesion process (Toyobo K.K., A-4300, film thickness: 188 μ m), and place it in 80 ℃ the drying oven 1 minute with scraping strip coating machine (No.20).With the ultraviolet ray of high voltage mercury lamp (120W/cm) irradiation, this UV lamp is 10cm apart from the height of film to resin combination on the film in air atmosphere, and the film gait of march is 5m/min, thereby obtains to have the film of solidified coating (10～15 μ m).

Table 3

Content (g)	Embodiment						Reference examples
								(C-1) (C-2) (C-3) (C-4) (C-5) (C-6) (H-1)	14 30	15 30	16 30	17 30	18 30	19 30	2 30
R-551 ^3 PRT-30 ^4 Irg.184 MEK ^*5	10 10 3 50	10 10 3 50	10 10 3 50	10 10 3 50	10 10 3 50	10 10 3 50	10 10 3 50

^*3:R-551; Nippon Kayaku Co., the product of Ltd., KAYARAD R-551; Bisphenol A-type gathers (n=4) oxyethyl group diacrylate

^*4:PET-30; Nippon Kayaku Co., the product of Ltd., KAYARAD PET-30; Pentaerythritol triacrylate

^*5:MEK; 2-butanone

Test case 2

Prepared film in embodiment 14～19 or the reference examples 2 is estimated by following items.The result is as shown in table 4.

(pencil hardness)

Use pencil cut machine to measure the pencil hardness of coated film according to JISK 5400.Particularly, pencil is arranged on the polyester film with solidified coating to be tested with 45, and on the top, applies the 1kg load, this film is scratched about 5mm to determine cut.This measurement is carried out five times, calculates the number of no marking film.

Estimate: 5 no markings in 5/5:5 time

All produce cut in 0/5:5 time

(wear-resisting test)

Applying 200g/cm ²Under the loading condiction, with film at Steel Wool ^#On 0000 reciprocal 10 times, the cut that detects by an unaided eye and produce.

Estimate 0: no marking

*: produce cut

(tackiness)

According to JIS K 5400, the distance with 1mm on film surface depicts 11 levels and vertical line, forms 100 grids.Behind the bonding Cellophane band of film surface (registered trademark), the sharp separation film shows binding property by the residual isolating grid number that do not have.

(curling)

The polyester film that will have cured film to be tested cuts into 5cm * 5cm, and places it in 80 ℃ the drying oven 1 hour, reduces to room temperature then.The height that on each bar limit of the four edges of measuring this square film on the horizontal stand, lifts, center line average (unit: mm) be set as measured value.Observe the curling 0mm of being of substrate at this moment.

(outward appearance)

Situation such as with the naked eye check surface crack, stress whitening and haze.

Estimate 0: good

△: slight crackle takes place

*: obvious crackle takes place

Table 4: the result of assessment

	Pencil hardness 3H	Wear resistance	Binding property	Curl	Outward appearance
						Embodiment 14 embodiment 15 embodiment 16 embodiment 17 embodiment 18 embodiment 19 reference examples 2	5/5 5/5 5/5 5/5 5/5 5/5 5/5	○ ○ ○ ○ ○ ○ ○	80 80 100 100 100 100 100	5 7 17 15 18 25 26	○ ○ ○ ○ ○ ○ △

Table 4 is the result point out: the film with photosensitive resin composition of the present invention coating demonstrates excellent character, comprising: high pencil hardness and wear resistance and take place hardly to curl and flawless almost.

Test case 3

(embodiment 20～25 and reference examples 3)

Use the resin combination that prepared compound (C-6) preparation has ratio of mixture as shown in table 5 in the prepared compound (C-1) and embodiment 6 among the embodiment 1, and the protection coating agent that is used as CD is estimated.Part expression weight part in table 5.

Table 5

Embodiment

Reference examples

Shrinking percentage (%) water-intake rate (%) transmissivity (%) warpage weather resistance when C-1 C-6 UX-6101 R-684 R-604 PHE LA Irg.184 viscosity (mPaS/25 ℃) is solidified

20 50 30 20 5 3700 5.3 1.1 80 ○ ○

21 50 25 25 5 2200 5.2 0.9 80 ○ ○

?22?60?40?5?2100?4.5?0.8?80?○?○

?23?50?40?10?5?2900?4.9?1.1?80?○?○

?24?50?40?10?5?3600?4.8?1.0?80?○?○

25 65 35 5 3100 4.2 0.8 80 ○ ○

3 20 70 10 5 2100 7.2 1.6 80 × ○

The abbreviation of each composition shown in the his-and-hers watches is as follows:

UX-6101: poly ester urethane type acrylate (molecular weight; 2700 ± 500), Nippon KayakuCo., the product of Ltd.

R-684: two (methyl) vinylformic acid, two ring pentyl esters, Nippon Kayaku Co., the product of Ltd.,

R-604: TriMethylolPropane(TMP) two (methyl) acrylate of the special valeral modification of hydroxyl, Nippon KayakuCo., the product of Ltd.

The PHE:(methyl) vinylformic acid phenoxy ethyl, Dai-ichi Kogyo Seiyaku Co., the product of Ltd

LA: lauryl acrylate, the product of NOF Corporation

Irg.184:1-hydroxy-cyclohexyl benzophenone, the product of Ciba Specialty Chemicals, light polymerization initiator

(viscosity)

The data of measuring with Brookfield viscometer are used as normal data

(shrinking percentage during curing)

By following formula (1), calculate the value of determining from the proportion (SG) of the proportion (SG) of liquid before 25 ℃ of curing and the film that after 25 ℃ of curing, makes.

Shrinking percentage during curing=(film SG-liquid SG)/film SG * 100 (1)

(water-intake rate)

By according to the resulting value of the method for JISK-7209 7.2.1, this value defined is a water-intake rate.

With this value defined is water-intake rate

(transmissivity)

The mensuration of transmissivity is as follows: on polycarbonate substrate, coating thickness is 100 ± 10 μ m to the employing spin-coating method, is cured with the UV radiation, with respect to poly-carbonic acid substrate, is determined at the transmissivity at 405nm place with resin-coated.

(warpage (wrap))

Use DVD with sputtered aluminum.Use on the DVD substrate of sputtered aluminum by using spin coater each composition that table 5 is listed to be coated on, thereby make the coated thin film that average film thickness is 100 μ m.Described coated thin film is 1000mJ/cm with integrated light intensity under being provided with highly for the UV irradiation lamp of 10cm (Japan Storage Battery Co., Ltd., CS-30L, 80w/cm, high voltage mercury lamp) ²Energy irradiation after, described coated thin film is solidified.Prepared testing plate is placed on sheet glass last 24 hour, carries out the warpage evaluation.

Zero: almost can not recognize warpage

△: when a side of testing plate press...withed one's finger, opposite side was to upper punch≤2mm.

*: when a side of testing plate press...withes one's finger, opposite side is to upper punch 〉=5mm.

(weather resistance)

Use used testing plate in the above-mentioned warpage evaluation, described testing plate was placed 500 hours under 85%RH and 80 ℃ of environment.The situation of reflectance coating detects by an unaided eye.

Zero: after bonding, observe immediately, on reflectance coating, do not find to change

△: on reflectance coating, observe the slight variation of color and luster and pin hole

*: on reflectance coating, observe the big variation of color and luster and pin hole

Resin combination of the present invention and solidify material thereof can make protection coating agent and the solidify material thereof that is used for high density compact disc; have good transparency and low water absorbable; and demonstrate high-durability and low warpage, be very useful as the CD that uses blue laser to read and/or to write usefulness.

Claims

1. protection coating agent that is used for CD, this coating agent comprises:

Photosensitive resin is made by isocyanate compound (A) or isocyanate compound (A ') mixture (B) reaction with multifunctional (methyl) acrylic compound,

Described isocyanate compound (A) is the reaction product that the alkylol cpd (b) of at least two hydroxyls is arranged in diisocyanate cpd (a) and its molecule; Described isocyanate compound (A ') derived from diisocyanate cpd (a), any in two isocyanate groups wherein forms the structure of isocyanurate ring,

The mixture (B) of described multifunctional (methyl) acrylic compound comprises multifunctional (methyl) acrylic compound with one or more hydroxyls and wherein all hydroxyl all esterified multifunctional (methyl) acrylic compound;

Light polymerization initiator (C);

Polymerisable compound (D).

2. the protection coating agent that is used for CD as claimed in claim 1 is characterized in that, the weight-average molecular weight that has the alkylol cpd (b) of at least two hydroxyls in its molecule is 100～1500.

3. the protection coating agent that is used for CD as claimed in claim 1 or 2; it is characterized in that multifunctional (methyl) acrylic compound with one or more hydroxyls is three (methyl) vinylformic acid pentaerythritol ester and/or five (methyl) vinylformic acid dipentaerythritol ester.

4. the protection coating agent that is used for CD as claimed in claim 1 or 2 is characterized in that mixture (B) is the mixture of pentaerythritol triacrylate and pentaerythritol tetracrylate.

5. the protection coating agent that is used for CD as claimed in claim 1 or 2; it is characterized in that described polymerizable compound (D) is to be selected from one or more following compounds: polyester (methyl) acrylate (D-1); carbamate (methyl) acrylate (D-2); epoxy type (methyl) acrylate (D-3); polyethers (methyl) acrylate (D-4); (methyl) alkyl acrylate or (methyl) vinylformic acid alkylene ester (D-5); (methyl) acrylate (D-6) with aromatic ring; (methyl) acrylate (D-7) with alicyclic structure; compound with maleimide base group; (methyl) acrylamide compound and unsaturated polyester.

6. the protection coating agent that is used for CD as claimed in claim 1 is characterized in that, the mixture (B) of described multifunctional (methyl) acrylic compound is the mixture of (methyl) acrylic compound of polyvalent alcohol.

7. solidify material, it is formed by any one described protection coating agent that is used for CD in the claim 1～6.

8. a film comprises solidify material as claimed in claim 7.

9. the solidify material that is used for the protection coating agent of CD as claimed in claim 7 is characterized in that, the water-intake rate of 25 ℃ of solidify material that record for≤2.0% and when solidifying shrinking percentage be≤6%.

10. as claim 7 or 9 described solidify material, it is characterized in that, is that the transmissivity of the solidify material medium blue laser of 50～150 μ m is 〉=70% at film thickness.

11. a CD, it has one deck such as claim 7,9 or 10 described solidify material.

12. CD as claimed in claim 11 is characterized in that, described curing material layer is structured in the recording light of CD and/or the light incident side of playback light.