CN107207643A - Resin sheet manufacture curing composition - Google Patents

Resin sheet manufacture curing composition Download PDF

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Publication number
CN107207643A
CN107207643A CN201580069101.7A CN201580069101A CN107207643A CN 107207643 A CN107207643 A CN 107207643A CN 201580069101 A CN201580069101 A CN 201580069101A CN 107207643 A CN107207643 A CN 107207643A
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China
Prior art keywords
composition
methyl
acrylate
resin sheet
compound
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CN201580069101.7A
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Chinese (zh)
Inventor
津田隆
神村浩之
小池信明
冈崎荣
冈崎荣一
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Toagosei Co Ltd
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Toagosei Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Abstract

There is provided a kind of hardness and flexural property for making resulting resin sheet excellent curing composition.A kind of resin sheet manufacture curing composition, it contains following (A) and (B) compositions, in the weight % of total amount 100 of (A) and (B) composition, contain the weight % of (A) composition 5~70 and the weight % of (B) composition 95~30.(A) composition：More than a kind in following (A1) compositions and (A2) composition, (A1) composition；Two (methyl) acrylate of straight-chain or branched alkylidene with carbon number 4~20, (A2) composition；Constitute PAG two (methyl) acrylate for adding up to 4~20 of the carbon number of polyoxy alkylidene.(B) composition：The compound with ethylenically unsaturated group in addition to (A) composition.

Description

Resin sheet manufacture curing composition
Technical field
The present invention relates to resin sheet manufacture curing composition, the resin sheet obtained by said composition can be preferred for The optics substrate such as liquid crystal display (LCD) and organic EL, can be more preferably used for for forming contact panel nesa coating Resin sheet, the application belongs to above-mentioned technical field.
It should be noted that in this specification, acryloyl group or methylacryloyl are expressed as (methyl) acryloyl group, In addition, acrylate or methacrylate are expressed as into (methyl) acrylate.
Background technology
In recent years, the gradually application touch control in large quantities in the mobile devices such as smart phone, tablet terminal, onboard navigation system The one-piece type liquid crystal display device of panel or the one-piece type organic EL display of contact panel.
In the past, as the transparent conducting film of contact panel, it is well known that tin indium oxide is formed with glass (following The conductive glass of film referred to as " ITO "), but because base material is glass, therefore flexible, poor in processability.Therefore, some purposes In the case of, from flexibility, processability, excellent impact resistance and light weight the advantages of and use with polyethylene terephthalate Ester piece is the transparent conductivity piece of base material.
On the other hand, the slim lightweight, transmissivity raising, the reduction of component cost of contact panel are contributed to from expectation Viewpoint is set out, and the shield for partly having employed the directly touch sensor such as formation ITO on cover glass is one-piece type tactile Control panel, i.e. so-called OGS (One Glass Solution, glass integrative solution).But, OGS types have such as Lower problem：Once cover glass ftractures, it will lead to not operate contact panel.
Therefore, it is proposed to directly form the contacts such as ITO on the resin sheet as the shield material of excellent impact resistance The so-called OPS (One Plastic Solution, resin integrative solution) of sensor.But, conventional acrylic acid It is piece, polycarbonate-based because case hardness is low and easily damages, toughness is also not enough sometimes in addition, may be because from outside Impulsive force and ftracture.
Patent document 1 discloses a kind of plastic member for being used to form nesa coating, it is to containing with alicyclic ring bone The double methyl methacrylate of frame and the light-cured type composition of sulfhydryl compound are carried out obtained from photocuring.
But, although appropriate toughness is imparted to solidfied material by coordinating sulfhydryl compound, but there is composition Working life (pot life) shorten the problem of, also there is the problem of case hardness, marresistance are also reduced.
Patent document 2 discloses that a kind of molded transparent resin of 50~500 μm of thickness, it is to containing with alicyclic ring knot Polyfunctional carbamate (methyl) acrylate, 2 functions (methyl) acrylate with alicyclic structure and the photopolymerization of structure The light-cured type composition of initiator is carried out obtained from photocuring.
But, due to the rigidity equal with glass can not be shown and there are the following problems：In nesa coating, metal electricity In heating process in the formation process of pole, the situation of bad order is produced.
To sum up, not yet find that there is the resin sheet of satisfied physical property as OPS with resin so far, be especially difficult to simultaneous Hardness and obdurability are turned round and look at, marresistance is also insufficient.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2002-161113 publications
Patent document 2：Japanese Unexamined Patent Publication 2007-56180 publications
The content of the invention
The invention problem to be solved
The present inventors is in order to have found the curing composition for making the hardness and flexural property of resulting resin sheet excellent And have made intensive studies.
Means for solving the problems
The present inventors has made intensive studies to solve above-mentioned problem, as a result finds, containing with specific carbon number The composition of two (methyl) acrylate can solve above-mentioned problem so that completing the present invention.
The present invention relates to a kind of resin sheet manufacture curing composition, it contains following (A) and (B) compositions, at (A) and (B) in the weight % of total amount 100 of composition, the weight % of (A) composition 5~70 and the weight % of (B) composition 95~30 are contained.
(A) composition：More than a kind in following (A1) compositions and (A2) composition
(A1) composition；Two (methyl) acrylate of straight-chain or branched alkylidene with carbon number 4~20
(A2) composition；Constitute PAG two (methyl) propylene for adding up to 4~20 of the carbon number of polyoxy alkylidene Acid esters
(B) composition：The compound with ethylenically unsaturated group in addition to (A) composition
As (A1) composition, BDO two (methyl) acrylate, 1,6- hexylene glycols two (methyl) are preferably selected from More than a kind in acrylate, (methyl) acrylate of 1,9- nonanediols two and neopentyl glycol two (methyl) acrylate.
As (A2) composition, polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylic acid are preferably selected from More than a kind in ester and polytetramethylene glycol two (methyl) acrylate.
As (B) composition, the compound with more than 3 (methyl) acryloyl groups is preferably comprised.In addition, as (B) into Point, reaction product preferably as organic multiple isocyanate and hydroxyl (methyl) acrylate and with more than 3 (methyl) The compound of acryloyl group, preferably in the weight % of total amount 100 of (A) and (B) composition, is contained with more than 20 weight % ratio There is the compound.
It is used as composition, the preferably composition also containing Photoepolymerizationinitiater initiater (D) or/and thermal polymerization (E).
As the solidfied material of composition, preferably pencil hardness is more than 3H.
As the resin sheet of the solidfied material containing composition, the thickness of preferred consolidation thing is 100 μm~5mm.
As the manufacture method of resin sheet, the manufacture method being preferably as follows：Make above-mentioned composition flow into by base material/be used for set Put in the mould of base material/base material composition of weir dike, then irradiate active energy beam from arbitrary substrate side.It is further excellent It is selected in the manufacture method heated after irradiation active energy beam.
In addition, as the manufacture method of resin sheet, being preferably as follows manufacture method：Above-mentioned composition is set to flow into by base material/use In the mould for setting base material/base material of weir dike to constitute, then heated.
The present invention is described in detail below.
Invention effect
According to the composition of the present invention, obtained resin sheet turns into hardness and the excellent resin sheet of flexural property.
In addition, obtained resin sheet turns into the resin sheet of excellent scratch resistance.
Brief description of the drawings
Fig. 1 is the figure of 1 example of mould used when representing the composition manufacture resin sheet using the present invention.
Embodiment
The present invention relates to a kind of resin sheet manufacture curing composition, it contains (A) and (B) composition, in (A) and (B) In the weight % of total amount 100 of composition, contain the weight % of (A) composition 5~70 and the weight % of (B) composition 95~30.
The details to each composition and composition are illustrated below.
(1. A) composition
(A) composition is more than a kind in (A1) composition and (A2) composition.
(A1) composition is two (methyl) acrylate of straight-chain with carbon number 4~20 or branched alkylidene.At this In invention, alkylidene refers to the substituent that the divalent of 2 hydrogen atoms is eliminated from alkane.
The compound for being just less than 3 for two (methyl) acrylate with straight-chain or branched alkylidene but carbon number For, the hardness of solidfied material, marresistance can be caused to become insufficient, on the other hand, carbon number can make for more than 21 compound Rigidity, the heat resistance of solidfied material decline.
As the straight-chain alkylidene of the divalent of the carbon number 4~20 in (A1) composition, preferably have the 1 of key in two ends, 4- butylidenes, 1,6- hexylidenes and 1,9- nonylene.
As the specific example of the compound, it can enumerate：BDO two (methyl) acrylate, 1,6- oneself two (methyl) acrylate of alcohol two and 1,9- nonanediol two (methyl) acrylate etc..
As the branched alkylidene of the divalent of the carbon number 4~20 in (A1) composition, preferably have new the penta of key in two ends Base (methyl isophthalic acid of 2- methyl -2,3- propylidene), 2- methyl isophthalic acids, the isobutylidene of 3- propylidene, the degree of polymerization below 5.
As the specific example of the compound, it can enumerate and most preferably with neopentyl glycol two (methyl) acrylate.
As (A1) composition, in these compounds, be preferably selected from BDO two (methyl) acrylate, 1,6- oneself In glycol two (methyl) acrylate, (methyl) acrylate of 1,9- nonanediols two and neopentyl glycol two (methyl) acrylate More than a kind.
As (A1) composition, in these compounds, further, 1,6- hexylene glycols two (methyl) propylene is more preferably selected from More than a kind in acid esters and 1,9- nonanediol two (methyl) acrylate.
(A2) composition is PAG two (methyl) propylene for adding up to 4~20 for the carbon number for constituting polyoxy alkylidene Acid esters.
Less than 3 are added up to regard to the carbon number for (methyl) acrylate of PAG two but composition polyoxy alkylidene Compound for, it can cause the hardness of solidfied material, marresistance to become insufficient, on the other hand, carbon number be more than 21 Compound can decline the rigidity of solidfied material, heat resistance.
As the example for adding up to 4~20 for the carbon number for constituting the polyoxy alkylidene in (A2) composition, it can enumerate：Oxygen second Polyoxypropylene base that polyoxyethylene groups that the repeat number of alkene unit is 2~6, the repeat number of oxypropylene units are 2~5, oxygen butylene The repeat number of base and oxygen butene units is 2~4 polybutylene base etc..As oxypropylene units, can be- OCH2CH2CH2- and-OCH2CH(CH3Any of)-, preferably-OCH2CH(CH3)-.
As the specific example of (A2) composition, it can enumerate：Diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, DPG two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, four propane diols two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, (methyl) acrylate of polytetramethylene glycol two and poly- (1- methyl butanediol) two (methyl) acrylate etc..
As (A2) composition, in these compounds, polyethylene glycol two (methyl) acrylate, polypropylene glycol two are preferably selected from More than a kind in (methyl) acrylate and polytetramethylene glycol two (methyl) acrylate.
As (A2) composition, in these compounds, further, polyethylene glycol two (methyl) acrylate is more preferably selected from With more than a kind in polypropylene glycol two (methyl) acrylate.
As (A) composition, a kind in above-mentioned (A1) composition and (A2) composition can be used only, can also be by two or more group Conjunction is used.
(2. B) composition
(B) composition is the compound with ethylenically unsaturated group in addition to (A) composition.
As the ethylenically unsaturated group in (B) composition, it can enumerate：(methyl) acryloyl group, vinyl and vinyl Ether etc., preferably (methyl) acryloyl group.
As (B) composition, compound (hereinafter referred to as " the simple function insatiable hunger with 1 ethylenically unsaturated group can be enumerated And compound ") and compound (hereinafter referred to as " multifunctional unsaturated compound ") with more than 2 ethylenically unsaturated groups Deng.
Each compound is specifically described below.
2-1. simple function unsaturated compounds
As simple function unsaturated compound, it can enumerate：Compound with 1 (methyl) acryloyl group is (hereinafter referred to as For " simple function (methyl) acrylate ") etc..
As the specific example of simple function (methyl) acrylate, it can enumerate：(methyl) isobornyl acrylate, (first Base) acrylic acid dicyclopentenyl ester, the ring pentyl ester of (methyl) acrylic acid two, (methyl) cyclohexyl acrylate, (methyl) acrylic acid front three Base cyclohexyl, (methyl) acrylic acid 1- adamantane esters, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) third Olefin(e) acid propyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) propylene The own ester of acid, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) third Olefin(e) acid 2- methoxy acrylates, (methyl) acrylic acid tetrahydrofurfuryl alcohol ester, (methyl) glycidyl acrylate, (methyl) acrylic acid Dimethylaminoethyl, (methyl) diethylaminoethyl acrylate, (methyl) benzyl acrylate, (methyl) allyl acrylate, (first Base) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylate, (1~4 rubs o-phenyl phenol ethylene oxide adduct Your addition product) (methyl) acrylate, p -cumylphenol ethylene oxide adduct (1~4 mole of addition product) (methyl) acrylic acid The adjacent phenyl phenyl ester of ester, (methyl) phenyl acrylate, (methyl) acrylic acid, (methyl) acrylic acid are to cumyl phenyl chloroformate, N- (methyl) third Alkene trimethylammonium hexahydrophthalic phthalimide, N- (methyl) acryloyl-oxyethyl tetrahydric phthalimide etc..
Can be the compound with various functional groups as simple function (methyl) acrylate.
As the example of the compound with carboxyl, it can enumerate：(methyl) acrylic acid, (methyl) acrylic acid gather oneself in Ester modified thing, the Michael's addition type polymer of (methyl) acrylic acid, (methyl) acrylic acid 2- hydroxyl ethyl esters and phthalic anhydride Addition product, the addition product of (methyl) acrylic acid 2- hydroxyl ethyl esters and succinic anhydride etc. containing carboxyl (methyl) acrylate etc..
As the example of the compound with hydroxyl, it can enumerate：(methyl) acrylate with hydroxyl.
As (methyl) acrylate with hydroxyl, it can enumerate：(methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) third Olefin(e) acid 2- hydroxypropyl acrylates, (methyl) hy-droxybutyl, (methyl) acrylic acid hydroxy pentane ester, the own ester of (methyl) acrylic acid hydroxyl and (first Base) (methyl) acrylic acid hydroxy alkyl ester such as acrylic acid hydroxyl monooctyl ester etc..
As the example of the compound with amide groups, it can enumerate：N- vinyl formamides, N- vinylacetyls Amine, NVP and (methyl) acrylamide based compound etc..
As the specific example of (methyl) acrylamide based compound, it can enumerate：N- methyl (methyl) acrylamide, The N- alkane such as N- ethyls (methyl) acrylamide, N- isopropyls (methyl) acrylamide and the N- tert-butyl groups (methyl) acrylamide Base acrylamide；
The N such as N, N- dimethyl (methyl) acrylamide and N, N- diethyl (methyl) acrylamide, N- dialkyl group propylene Acid amides；
N- ethoxys (methyl) acrylamide, N- methylols (methyl) acrylamide, N- methoxies (methyl) third The N- alkoxy alkane such as acrylamide and N- butoxymethyls (methyl) acrylamide, N- methoxy ethyls (methyl) acrylamide Base (methyl) acrylamide；And (methyl) acryloyl morpholine etc..
As the example of the compound with carbamate groups, it can enumerate：(methyl) third of Ju oxazolidine ketone groups Olefin(e) acid ester etc., as its specific example, can be enumerated：Acrylic acid 2- (2- oxo -3- oxazoles alkyl) ethyl ester etc..
As the example of the compound with imide, it can enumerate：Compound with dimaleoyl imino.As Compound with dimaleoyl imino, can be enumerated：(methyl) acrylate with hexahydrophthalic phthalimide base and (methyl) acrylate with tetrahydric phthalimide base etc..It is used as (the first with hexahydrophthalic phthalimide base Base) acrylate specific example, can enumerate：N- (methyl) acryloyl-oxyethyl hexahydrophthalic phthalimide etc..Make For the example of (methyl) acrylate with tetrahydric phthalimide base, it can enumerate：N- (methyl) acryloxy Ethyl tetrahydric phthalimide etc..
The multifunctional unsaturated compounds of 2-2.
On multifunctional unsaturated compound, the compound (hereinafter referred to as " 2 with 2 (methyl) acryloyl groups is used as Function (methyl) acrylate ".Hereinafter, the compound with more than 3 (methyl) acryloyl groups is similarly expressed as " zero official Energy (methyl) acrylate ".), it can enumerate：Two (methyl) acrylate and bisphenol-A two of bisphenol-A epoxy alkane addition product (methyl) acrylate etc. has 2 functions (methyl) acrylate of aromatic backbone；
Ethylene glycol two (methyl) acrylate, (methyl) acrylate of propane diols two and neopentyl glycol two (methyl) propylene 2 functions (methyl) acrylate with aliphatic skeleton beyond acid esters etc. (A) composition；
3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate；
Dihydroxymethyl tristane two (methyl) acrylate, (methyl) acrylate of cyclohexanedimethanol two and spiral shell glycol Two (methyl) acrylate etc. have 2 functions (methyl) acrylate of alicyclic skeleton；
It should be noted that as the alkylene oxide adducts in above-mentioned, can enumerate：Ethylene oxide adduct and epoxy Propane addition product etc..
As multifunctional (methyl) acrylate, in addition to the foregoing, it can also enumerate：Carbamate (methyl) propylene Acid esters, polyester (methyl) acrylate, epoxy (methyl) acrylate and polyethers (methyl) acrylate etc..
These compounds are illustrated below.
2-2-1. carbamates (methyl) acrylate
As multifunctional (methyl) acrylate, preferably as with amino-formate bond and with more than 2 (methyl) Carbamate (methyl) acrylate (hereinafter referred to as " (B1) composition ") of the compound of acryloyl group.
As (B1) composition, it can enumerate：Polyalcohol, organic multiple isocyanate and hydroxyl (methyl) acrylate it is anti- Answer product (hereinafter referred to as " (B1-1) composition "), and organic multiple isocyanate and hydroxyl (methyl) acrylate reaction Product (hereinafter referred to as " (B1-2) composition ") etc..
(B1-1) composition and (B1-2) composition are illustrated below.
1) (B1-1) composition
(B1-1) composition is the reaction product of polyalcohol, organic multiple isocyanate and hydroxyl (methyl) acrylate.
It is used as the polyalcohol in (B1-1) composition, preferred diol.
As glycol, preferably low molecular weight diols, the glycol with polyester backbone, the glycol with polyether skeleton and have The glycol of polycarbonate backbone.
As low molecular weight diols, it can enumerate：Ethylene glycol, propane diols, cyclohexanedimethanol, neopentyl glycol, 3- first Base -1,5-PD, 1,6- hexylene glycols etc..
As the glycol with polyester backbone, it can enumerate：The glycol such as above-mentioned low molecular weight diols or polycaprolactone glycol Esterification reaction product of composition and the sour composition such as dicarboxylic acids or its acid anhydrides etc..
As dicarboxylic acids or its acid anhydrides, it can enumerate：Adipic acid, butanedioic acid, phthalic acid, tetrahydrophthalic acid, Hexahydrophthalic acid and terephthalic acid (TPA) etc., and their acid anhydrides etc..
As PTMEG, it can enumerate：Polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc..
As PCDL, it can enumerate：The bis-phenols such as above-mentioned low molecular weight diols or/and bisphenol-A and ethene carbonic acid Reaction product of the dialkyl carbonate such as ester and dibutyl carbonate etc..
As organic multiple isocyanate, it can enumerate：Aliphatic polyisocyante without ester ring type group is (below, Referred to as " aliphatic polyisocyante "), (hereinafter referred to as " ester ring type is more for the aliphatic polyisocyante with ester ring type group Isocyanates "), the polyisocyanates with heterocycle and aromatic polyisocyanate etc..
As aliphatic polyisocyante, it can enumerate：Hexamethylene diisocyanate, tetramethylene diisocyanate, Trimethyl hexamethylene diisocyanate and lysine diisocyanate etc..
As ester ring type polyisocyanates, it can enumerate：Hydrogenated toluene diisocyanate, hydrogenation 4,4 '-diphenyl methane Diisocyanate, hydrogenated xylene diisocyanate, HMDI, isophorone diisocyanate Ester and IPDI trimer etc..
As aromatic diisocyanate, it can enumerate：Toluene di-isocyanate(TDI), 4,4 '-diphenylmethane diisocyanate Ester, XDI, PPDI and 1,5- naphthalene diisocyanate etc..
In the present invention, as organic multiple isocyanate, go out from the viewpoint that the physical characteristic of solidfied material is excellent, xanthochromia is few Hair, preferred aliphat polyisocyanates.
It is used as hydroxyl (methyl) acrylate, preferably hydroxyl list (methyl) acrylate.
As hydroxyl list (methyl) acrylate, it can enumerate：(methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) propylene Sour 2- hydroxypropyl acrylates, (methyl) hy-droxybutyl, (methyl) acrylic acid hydroxy pentane ester, the own ester of (methyl) acrylic acid hydroxyl and (methyl) Acrylic acid hydroxyl monooctyl ester etc. (methyl) hydroxyalkyl acrylates etc..
2) (B1-2) composition
(B1-2) composition is the reaction product of organic multiple isocyanate and hydroxyl (methyl) acrylate, is known as The compound of carabamate adducts.
By using (B1-2) composition as (B) composition so as to which crosslink density is improved, heat resistance improves, therefore is preferred 's.
In (B1-2) composition, as organic multiple isocyanate and hydroxyl (methyl) acrylate, it can enumerate above-mentioned Compound.
In (B1-2) composition, as hydroxyl (methyl) acrylate, it can also use with hydroxyl and more than 2 The compound (hereinafter referred to as " multifunctional (methyl) acrylate of hydroxyl ") of (methyl) acryloyl group.
Using the organic multiple isocyanate and multifunctional (methyl) acrylate of hydroxyl (hereinafter referred to as " (B1-2-1) Composition ") be used as (B1-2) composition, then crosslink density is improved, heat resistance is improved and hardness, resistance to abrasion and marresistance are also excellent It is different, therefore be preferred.
As multifunctional (methyl) acrylate of hydroxyl, various compounds can be used, specifically, can be enumerated： Trimethylolpropane two (methyl) acrylate, two or three (methyl) acrylate of pentaerythrite, double trimethylolpropane Two, three, four or five (methyl) acrylate of two or three (methyl) acrylate and dipentaerythritol etc..
Among these, from the viewpoint of the hardness of cured film, abrasion performance and excellent scratch resistance, preferably with 3 The above (methyl) acryloyl group and the compound with 1 hydroxyl, specifically, can be enumerated：Pentaerythrite three (methyl) third Olefin(e) acid ester, (methyl) acrylate of double trimethylolpropane three and dipentaerythritol five (methyl) acrylate etc..
In these compounds, from the viewpoint of the solidfied material warpage that can prevent from obtaining, the more preferably (first of pentaerythrite three Base) acrylate.
In the manufacture of (B1-2-1) composition, multifunctional (methyl) acrylate of hydroxyl as raw material is usually to contain There is the mixture of multifunctional (methyl) acrylate of hydroxyl and multifunctional (methyl) acrylate without hydroxyl, as (B1-2-1) composition, can also utilize the material manufactured using the mixture.
Specifically, it can enumerate：(methyl) acrylate of trimethylolpropane two and trimethylolpropane tris (methyl) The mixture of acrylate, two trimethylolpropane tris (methyl) acrylate and two trimethylolpropane four (methyl) acrylic acid The mixture and (methyl) acrylate of dipentaerythritol five of ester and the mixture of dipentaerythritol six (methyl) acrylate Deng.
As other preferred compounds of (B1-2) composition, it can enumerate：It is organic with more than 3 NCOs The reaction product (hereinafter referred to as " (B1-2-2) composition ") of polyisocyanates and hydroxyl list (methyl) acrylate.
As hydroxyl list (methyl) acrylate in (B1-2-2) composition, it can enumerate：It is same with above-claimed cpd The compound of sample.
As the example of the organic multiple isocyanate with more than 3 NCOs, it can enumerate：Above-mentioned hexa-methylene Diisocyanate trimer and IPDI trimer etc..
As the preferred example of (B1-2-2) composition, it can enumerate：Hexamethylene diisocyanate trimer and propylene Addition reaction product of sour hydroxy butyl ester etc..
In addition, as (B1-2) composition, more preferably as organic multiple isocyanate and hydroxyl (methyl) acrylate Reaction product, compound with more than 3 (methyl) acryloyl groups.The compound is tieed up by the crosslink density of solidfied material Rigidity is held, while having high obdurability.
As the example of the compound, it can enumerate：Above-mentioned (B1-2-1) composition and (B1-2-2) composition.
3) manufacture method of (B1) composition
On (B1) composition, (B1-1) composition passes through polyalcohol, organic multiple isocyanate and hydroxyl (methyl) acrylic acid The addition reaction of ester is manufactured, addition that (B1-2) composition passes through organic multiple isocyanate and hydroxyl (methyl) acrylate React to manufacture.
Even if the addition reaction can also be carried out under without catalyst, but in order that reaction efficiently progress, can also add two Amine system catalyst such as the tin such as dibutyl tin laurate series catalysts, triethylamine etc..
2-2-2. polyester (methyl) acrylate
As polyester (methyl) acrylate, it can enumerate：Dehydration condensation of polyester-diol and (methyl) acrylic acid etc..
Here, as polyester-diol, it can enumerate：Reaction product of glycol and dicarboxylic acids or its acid anhydrides etc..
As glycol, it can enumerate：Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propane diols, DPG, tripropylene glycol, polypropylene glycol, butanediol, polytetramethylene glycol, tetramethylene glycol, hexamethylene glycol, new penta 2 Alcohol, cyclohexanedimethanol, 3- methyl isophthalic acids, low molecular weight diols and their epoxy such as 5- pentanediols, 1,6- hexylene glycols Alkane addition product etc..
As dicarboxylic acids or its acid anhydrides, it can enumerate：Phthalic acid, M-phthalic acid, terephthalic acid (TPA), adipic acid, The dicarboxylic acids such as butanedioic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid and they Acid anhydrides etc..
2-2-3. epoxies (methyl) acrylate
Epoxy (methyl) acrylate is (methyl) acrylic acid is carried out compound obtained by addition reaction with epoxy resin. As epoxy resin, it can enumerate：Aromatic epoxy resin and aliphatic epoxy resin etc..
As aromatic epoxy resin, specifically, it can enumerate：Resorcinolformaldehyde resin, hydroquinones two Glycidol ether；Bisphenol-A, Bisphenol F, bisphenol S, the diglycidyl ether of bisphenol fluorene or its alkylene oxide adducts；Phenol novolac The phenol aldehyde type epoxy resin such as type epoxy resin and cresol novolak type epoxy resin；Glycidyl phthalimide；Adjacent benzene Dicarboxylic acid diglycidyl ester etc..
As aliphatic epoxy resin, specifically, it can enumerate：Ethylene glycol, propane diols, BDO and 1,6- The diglycidyl ether of the aklylene glycols such as hexylene glycol；The polyalkylenes such as the diglycidyl ether of polyethylene glycol and polypropylene glycol two The diglycidyl ether of alcohol；The diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adducts；Hydrogenation is double Phenol A and its alkylene oxide adducts diglycidyl ether；Tetrahydrophthalic acid 2-glycidyl ester etc..
In above-mentioned, as the epoxyalkane in alkylene oxide adducts, optimization ethylene oxide and expoxy propane etc..
2-2-3. polyethers (methyl) acrylate
As polyethers (methyl) acrylate oligomer, there is PAG (methyl) diacrylate, can enumerate： Polyethylene glycol two (methyl) acrylate, (methyl) acrylate of polypropylene glycol two and polytetramethylene glycol two (methyl) propylene Acid esters etc..
2-3. brief summary
As (B) composition, it can enumerate：1 kind in above-claimed cpd can be used only, two or more can also be combined Use.
As (B) composition, the reasons why from rigidity and the excellent heat resistance of solidfied material, in above-claimed cpd, preferably 3 officials Can more than (methyl) acrylate, it is further preferred that being the anti-of organic multiple isocyanate and hydroxyl (methyl) acrylate Answer product and with the compound of more than 3 (methyl) acryloyl groups.
In the case of containing (methyl) acrylate more than 3 functions as (B) composition, in (B) composition, preferably comprise More than 20 weight %.In addition, (methyl) acrylate more than 3 functions is preferably in the weight of total amount 100 of (A) and (B) composition Measure and contain more than 20 weight % in %.
In addition, as simple function (methyl) acrylate, preferably (methyl) isobornyl acrylate etc. has ester ring type bone Simple function (methyl) acrylate of frame, also, as 2 functions (methyl) acrylate, preferably：Dihydroxymethyl tristane two (methyl) acrylate, (methyl) acrylate of cyclohexanedimethanol two and spiral shell glycol two (methyl) acrylate etc. have alicyclic ring 2 functions (methyl) acrylate of formula skeleton.
3. resin sheet manufacture curing composition
The present invention relates to a kind of resin sheet manufacture curing composition, it is the composition containing (A) and (B) composition, In the weight % of total amount 100 of (A) and (B) composition (following, these are collectively referred to as " curability composition "), contain (A) composition 5 ~the 70 weight % and weight % of (B) composition 95~30.
When the containing ratio of (A) composition is less than the containing ratio of 5 weight % or (B) composition more than 95 weight %, solidification The marresistance of thing can become insufficient.On the other hand, (A) composition containing ratio more than 70 weight % or (B) composition When containing ratio is less than 30 weight, rigidity, heat resistance can become insufficient.
As the containing ratio of (A) and (B) composition, it is respectively preferably with respect to total 100 weight % of curability composition 10~50 weight % and 90~50 weight %.
As the manufacture method of composition, conventionally, for example can by (A) and (B) composition, as needed The other compositions stirring mixing used, so as to manufacture.
The viscosity of composition can suitably be set according to purpose, preferably 50~10,000mPas.
It should be noted that in the present invention, viscosity refers to the value determined using E types viscosimeter at 25 DEG C.
The composition of the present invention can be used as active energy ray-curable composition and thermohardening type composition.
The composition of the present invention is used as required composition using above-mentioned (A) and (B) composition, but it is also possible to coordinate various according to purpose Composition.
As other compositions, specifically, it can enumerate：Photoepolymerizationinitiater initiater (hereinafter referred to as " (C) composition "), hot polymerization Initiator (hereinafter referred to as " (D) composition "), organic solvent, plasticizer, polymerization inhibitor or/and antioxidant, light resistance is closed to improve Agent and compound (hereinafter referred to as " multi-functional thiol ") with more than 2 sulfydryls etc..
Hereinafter, these compositions are illustrated.It should be noted that composition described later can be used only a kind, also may be used in addition So that two or more to be applied in combination.
The other compositions of 3-1.
1) (C) composition
(C) composition is Photoepolymerizationinitiater initiater.
(C) composition that coordinates when composition is using ultraviolet and luminous ray as active energy beam.Using electricity When beamlet is as active energy beam, it is not necessary to coordinate, but in order to improve curability, it can also coordinate on a small quantity as needed.
As (C) composition, it can enumerate：Benzil dimethyl ketal, benzil, benzoin, benzoin ethyl ether, benzoin Isopropyl ether, benzoin isobutyl ether, 1- hydroxycyclohexylphenylketones, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 1- [4- (2- hydroxyl-oxethyls)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, oligomeric [2- hydroxyls Base -2- methyl isophthalic acids-[4-1- (methyl ethylene) phenyl] acetone, 2- hydroxyls -1- [4- [4- (2- hydroxyls - 2- methyl-propanoyls)-benzyl]-phenyl] -2- methylpropane -1- ketone, 2- methyl isophthalic acids-[4- (methyl mercapto)] Phenyl] -2- morpholino propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls) butane - 1- ketone, 2- dimethylaminos -2- (4- methyl-benzyls) -1- (4- morpholines -4- bases-phenyl)-butane -1- The aromatic ketones such as ketone, Adeka Optomer N-1414 ((strain) ADEKA systems), phenylglyoxalates methyl esters, EAQ, phenanthrenequione Compound；
Benzophenone, 2 methyl benzophenone, 3- methyl benzophenones, 4- methyl benzophenones, 2,4,6- front threes Base benzophenone, 4- phenyl benzophenones, 4- (methylphenyl-sulfanyl) phenyls methane, methyl -2- benzophenone, 1- [4- (4- benzoylphenyl sulfydryl (Japaneses：Off ェ ニ Le ス Le Off ァ ニ Le)) phenyl] -2- methyl -2- (4- first Base phenyl sulfonyl) propane -1- ketone, 4,4 '-bis- (dimethylamino) benzophenone, 4,4 '-bis- (diethylaminos) two Benzophenone, N, N '-tetramethyl -4,4 '-diaminobenzophenone, N, N '-tetraethyl -4,4 '-diaminobenzophenone With the benzophenone based compound such as 4- methoxyl groups -4 '-dimethylamino benzophenone；
Double (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, the oxidation of 2,4,6- trimethyl benzoyl diphenyl bases Phosphine, ethyl-(2,4,6- trimethylbenzoyl) phenyl phosphite (Japanese：Off ェ ニ Le Off ォ ス Off ィ ネ ー ト) and it is double (2,6- Dimethoxybenzoyl) -2, the acylphosphine oxide compound such as 4,4- trimethylpentylphosphine oxides；
The chloro- 4- propyl group thioxanthene of thioxanthones, CTX, 2,4- diethyl thioxanthones, isopropyl thioxanthone, 1- Ketone, 3- [3,4- dimethyl -9- oxo -9H- thioxanthones -2- bases] epoxide] -2- hydroxypropyls-N, N, N- front three The thioxanthones based compound such as ammonium chloride and fluoro thioxanthones；
The acridone based compounds such as acridone, 10- butyl -2- chloro-acridine ketone；
1,2- octanedione 1- [4- (thiophenyl) -2- (o-benzoyl oxime)] and ethyl ketone 1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] the oxime esters such as -1- (O- acetyl group oxime)；
2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazoles dimer, 2- (Chloro-O-Phenyl)-(meta-methoxies of 4,5- bis- Phenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5- phenylimidazoles dimer, 2- (o-methoxyphenyl) -4,5- bis- Phenylimidazole dimer, 2- (p-methoxyphenyl) -4,5- diphenyl-imidazoles dimer, 2,4- bis- are (to methoxybenzene Base) -5- phenylimidazoles dimer and 2- (2,4- Dimethoxyphenyl) -4,5- diphenyl-imidazole dimers etc. 2,4, 5- triarylimidazoles dimers；And the acridine derivatives such as 9- phenylacridines and double (9, the 9 '-acridinyl) heptane of 1,7- etc..
As (C) composition, in addition to the foregoing, the Photoepolymerizationinitiater initiater that molecular weight is more than 350 can also be used.Just divide For the Photoepolymerizationinitiater initiater of son amount more than 350, the resin sheet obtained by the analyte after light irradiation will not be coloured, in addition When for manufacturing transparent and electrically conductive film, when carrying out the vacuum film formation of transparent conductor layer, outgassing will not also occur for analyte (Japanese：ア ウ ト ガ ス), it therefore can reach high vacuum in a short time, can prevent the film quality of conductor layer from declining and difficult With the situation of low resistance.
As (C) composition, as long as molecular weight starts to gather for more than 350 and by the light of ultraviolet, luminous ray etc. The compound of conjunction can then use various compounds.
As the specific example of (C) composition, it can enumerate：Polymer of hydroxy-ketone etc., for example, can enumerate following formula (1) Shown compound etc..The compound is also preferred in terms of with the excellent compatibility of (A)~(C) compositions.
[changing 1]
In formula (1), R1Represent hydrogen atom or methyl, R2Alkyl is represented, n represents 2~5 number.
R2As alkyl it is preferred that the low alkyl group such as methyl, ethyl and propyl group.
As the specific example of the compound shown in formula (1), it can enumerate：Oligomeric (2- hydroxy-2-methyls -1- (4- (1- methyl ethylenes) phenyl) acetone etc..
The compound is on sale in the market, it is known to such as ESACURE KIP 150 (Lamberti company systems). ESACURE KIP 150 be compound shown in above-mentioned formula (1) in, R1For hydrogen atom or methyl, R2For methyl, n be 2~3 number, And the compound of the molecular weight with [(204.3 × n+16.0) or (204.3 × n+30.1)].
As compound other than the above, it can enumerate：2- [2- oxo -2- phenylacetyl epoxides ethyoxyl] ethyl ester With hydroxyphenylacetic acids (Japanese：オ キ シ Off ェ ニ Le jealous woman acid) etc..
The compound is on sale in the market, it is known to Irgacure754 (BASF AG's system).Irgacure754 is oxybenzene Guanidine-acetic acid 2- [2- oxo -2- phenylacetyl epoxides ethyoxyl] ethyl ester and hydroxyphenylacetic acids 2- (2- hydroxyl-oxethyls) The mixture of ethyl ester.
As the compounding ratio of (C) composition, relative to the parts by weight of total amount 100 of curability composition, preferably 0.01~10 Parts by weight, more preferably 0.1~5 parts by weight.
By the way that the compounding ratio of (C) composition is set to more than 0.01 weight %, so as to appropriate ultraviolet or can See that amount light solidifies composition, productivity ratio can be improved, on the other hand by being set to below 10 parts by weight, solidfied material can be made Weatherability, the transparency it is excellent.
2) (D) composition
Using composition as thermohardening type composition in use, (D) composition (thermal polymerization) can be coordinated.
As thermal polymerization, various compounds, preferably organic peroxide and azo series initiators can be used.
As the specific example of organic peroxide, it can enumerate：1,1- bis(t-butylperoxy) 2- methyl cyclohexanes Double (the tertiary hexyl peroxies) -3 of alkane, 1,1-, 3,5- trimethyl-cyclohexanes, 1,1- double (tertiary hexyl peroxy) hexamethylene, 1, 1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes, 1,1- bis(t-butylperoxy) cyclohexanes, 2,2- are double (4,4- dibutyl peroxidating cyclohexyl) propane, 1,1- bis(t-butylperoxy)s cyclododecane, dilauroyl peroxide, uncle Hexyl isopropyl peroxide monocarbonate, peroxidating Malaysia tert-butyl acrylate, tert-butyl hydroperoxide -3,5,5- tri-methyl hexanoic acids The tertiary own ester of ester, the peroxylauric acid tert-butyl ester, tert-Butyl peroxypivalate, peroxidating neopentanoic acid, 2,5- dimethyl -2, 5- bis- (toluoyl base peroxy) hexane, t-butylperoxyisopropyl monocarbonate, tert-butyl hydroperoxide 2- ethyl hexyls The tertiary own ester of base monocarbonate, perbenzoic acid, 2,5-, bis--methyl -2,5- bis- (benzoylperoxy) hexane, peroxide Change tert-butyl acetate, 2,2- bis(t-butylperoxy)s butane, peroxidized t-butyl perbenzoate, normal-butyl 4, double (the tertiary fourths of 4- Base peroxy) valerate, peroxidating M-phthalic acid di tert butyl carbonate, α, α '-bis(t-butylperoxy) diisopropyl benzene, two Cumyl peroxide, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hexane, tert-butyl cumyl peroxide, two tertiary fourths Base peroxide, hydrogen peroxide are to Meng's alkane, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hex- 3- alkynes, peroxidating Hydrogen diisopropylbenzene (DIPB), tert-butyl group trimethyl silyl peroxide, 1,1,3,3- tetramethyl butyl hydroperoxide, hydroperoxidation Cumene, tertiary hexyl hydrogen peroxide, TBHP etc..
As the specific example of Azo, it can enumerate：1,1 '-azo double (hexamethylene -1- nitriles), 2- (carbamoyl azo) isobutyronitrile, 2- phenylazo -4- methoxyl groups -2,4- methyl pentane nitrile, the tertiary octane of azo two, Tertiary butane of azo two etc..
These may be used alone, or two or more kinds may be used in combination.In addition, organic peroxide can also pass through Combined with reducing agent and carry out redox reaction.
As the usage rate of (D) composition, relative to the parts by weight of curability composition total amount 100 preferably 10 parts by weight with Under.
When thermal polymerization is used alone, carried out according to the conventional meanses of common free radical thermal polymerization, it is some In the case of, it can also be applied in combination with Photoepolymerizationinitiater initiater, can be further for the mesh for improving reactivity after photocuring And carry out heat cure.
3) organic solvent
In the composition of the present invention, organic solvent can be coordinated to purposes such as the screening characteristics of base material for improving.
But, when obtained resin sheet is used for into transparent and electrically conductive film purposes, preferably without organic solvent.
As the specific example of organic solvent, it can enumerate：N-hexane, benzene,toluene,xylene, ethylbenzene and hexamethylene etc. Hydrocarbon system solvent；
Methanol, ethanol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, isobutanol, 2-methyl cellosolve, 2- second Ethoxy-ethanol, 2- (methoxymethoxy) ethanol, 2- isopropoxide ethanols, butoxy ethanol, 2- isoamoxy ethanol, 2- hexyloxyethanols, 2- phenoxetols, 2- BOEs, furfuryl alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol list first Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1- methoxy-2-propanols, 1- ethyoxyl -2- propyl alcohol and the third two The alcohol series solvents such as alcohol monomethyl ether；
Tetrahydrofuran, dioxanes, glycol dimethyl ether, ethylene glycol diethyl ether, butyl cellosolve, double (2- methoxyl group second Base) ether series solvent such as ether, double (2- ethoxyethyl groups) ethers and double (2- butoxyethyl groups) ethers；
Acetone, MEK, methyl n-propyl ketone, metacetone, butyl methyl ketone, methyl iso-butyl ketone (MIBK), methyl amyl ketone, The ketone series solvents such as diη-propyl ketone, DIBK, phorone, isophorone, cyclopentanone, cyclohexanone and methyl cyclohexanone；
Ethyl acetate, butyl acetate, isobutyl acetate, methyl glycol acetate, propylene glycol methyl ether acetate, second The ester series solvents such as sour cellosolve；
DMF, DMA, dimethyl sulfoxide (DMSO), METHYLPYRROLIDONE, The aprotic polar solvents such as gamma-butyrolacton.
As the ratio of organic solvent, can be appropriately configured, it is preferred that in the composition preferably 90 weight % with Under, more preferably below 80 weight %.
4) plasticizer
For assigning flexibility to solidfied material, improving brittle purpose, plasticizer can be added.
As the specific example of plasticizer, it can enumerate：The neighbours such as dioctyl phthalate, diisononyl phthalate Dialkyl；The hexanedioic acid dialkyl esters such as dioctyl adipate, sebacate, azelate, tricresyl phosphate Deng phosphate；The liquids such as the liquid such as polypropylene glycol PPG, polycaprolactone glycol, 3- methyl pentanediol adipate esters are gathered Ester polyol etc..Furthermore it is possible to enumerate the soft acrylic based polymer of number-average molecular weight 10, less than 000 etc..
As the compounding ratio of these plasticizer, it can be appropriately configured, relative to total 100 weights of curability composition Measure below part preferably 30 parts by weight, below more preferably 20 parts by weight.
By being set to below 30 parts by weight, so as to so that intensity, excellent heat resistance.
5) polymerization inhibitor or/and antioxidant
Polymerization inhibitor or/and antioxidant can be added in order to improve in storage stability, composition of the invention.
As polymerization inhibitor, preferably hydroquinones, hydroquinone monomethyl ether, 2,6- di-tert-butyl-4-methy phenols, with And various phenol antioxidants, but it is also possible to add sulphur system auxiliary antioxidant, phosphorus system auxiliary antioxidant etc..
Total amount 100 parts by weight of the total compounding ratio of these polymerization inhibitors or/and antioxidant relative to curability composition It is preferred that below 3 parts by weight, below more preferably 0.5 parts by weight.
6) light fastness enhancer
In the composition of the present invention, the light fastness enhancers such as ultra-violet absorber, light stabilizer can be added.
As ultra-violet absorber, it can enumerate：2- (2'- hydroxy-5-methyl bases phenyl) BTA, 2- (2'- Hydroxyl -3', 5'- di-tert-butyl-phenyl) BTA, 2- (the 2'- hydroxyl -3'- tert-butyl group -5'- aminomethyl phenyls) benzene And the benzotriazole cpd such as triazole；
The triazines such as 2,4- double (2,4- 3,5-dimethylphenyl) -6- (the iso- octyloxyphenyls of 2- hydroxyls -4-) s-triazine Compound；
2,4- dihydroxy-benzophenone, BP-3,2- hydroxyl -4- methoxies Base -4'- methyl benzophenones, 2,2'- dihydroxy -4- methoxy benzophenones, 2,4,4'- trihydroxybenzophenones, 2,2', 4,4'- tetrahydroxybenzophenones, 2,3,4,4'- tetrahydroxybenzophenones, 2,3', 4,4'- tetrahydroxybenzophenones, Or the benzophenone cpd such as 2,2'- dihydroxy -4,4'- dimethoxy-benzophenones etc..
As photostability agent, it can enumerate：N, N '-bis- (2,2,6,6- tetramethyl -4- piperidyls)-N, N ' - Diformyl hexamethylene diamine, double (1,2,6,6-) pentamethyl -4- piperidyls) -2- (3,5- di-t-butyl -4- hydroxyl benzyls Base) the low molecule amount such as -2- n-butylmalonic acids ester, double (1,2,2,6,6- pentamethyl -4- piperidyls) sebacates is obstructed Amines；N, N '-bis- (2,2,6,6- tetramethyl -4- piperidyls)-N, N '-diformyl hexamethylene diamine, it is double (1,2,2, 6,6- pentamethyl -4- piperidyls) the amine system light stabilizer that is obstructed such as the high molecular weight hindered amine compound such as sebacate.
Total amount 100 parts by weight preferably 0~5 weight of the compounding ratio of light fastness enhancer relative to curability composition Part, more preferably 0~1 parts by weight.
7) multi-functional thiol
For the purpose for the cure shrinkage for preventing composition solidfied material, the purpose of imparting obdurability, it can match somebody with somebody as needed Close multi-functional thiol.
As multi-functional thiol, as long as the compound with more than 2 sulfydryls can then use various compounds.
It can enumerate for example：The mercaptoacetate of pentaerythrite four, the mercaptopropionic acid ester of pentaerythrite four etc..
As the ratio of multi-functional thiol, below the parts by weight of curability composition 100 preferably 20 parts by weight, more preferably Below 10 parts by weight, below particularly preferred 5 parts by weight.By the way that the ratio is set to below 20 parts by weight, obtained by can preventing The heat resistance of solidfied material, rigid reduction.
8) other compositions other than the above
In the composition of the present invention, in addition to above-mentioned other compositions, releasing agent, filler and dissolubility can also be coordinated poly- Compound etc..
Releasing agent, which is in order at, makes obtained resin sheet easily coordinate from the purpose that base material is stripped.As releasing agent, only It can be stripped from base material and fluid,matching and solidfied material will not be muddy, then can use various surfactants.Example can be enumerated Such as：The cationic surfactants such as the anion surfactants such as alkyl benzene sulphonate, alkylammonium salt, polyoxyethylene alkyl ether etc. are non- The amphoteric surfactantes such as ionic surface active agent, alkyl carboxyl glycine betaine, and contain fluorine, surfactant of silicon etc..
Filler is in order at the purpose of the mechanical properties of the resin sheet obtained by improving and coordinated.As filler, it can make With any number of in inorganic compound and organic compound.As inorganic compound, silica and aluminum oxide etc. can be enumerated. As organic compound, polymer can be used.As filler, it is used for light in the resin sheet that will be obtained by the composition of the present invention When learning purposes, the filler that will not preferably cause optics physical property to reduce.
Dissolubility polymer is in order at the purpose of the mechanical properties of the resin sheet obtained by improving and coordinated.Dissolubility is gathered Compound refers to the polymer for being dissolved in composition.In the present invention, the polymer insoluble in composition is referred to as filler, to carry out Difference.
As the compounding ratio of above-mentioned other compounds, relative to the parts by weight of curability composition 100 preferably 20 parts by weight with Under, below more preferably 10 parts by weight.
3-2. solidfied material physical property
As the physical property of the solidfied material of the composition in the present invention, pencil hardness is more than 3H.
It is used as pencil hardness, preferably more than 5, more preferably more than 7.
It should be noted that the pencil hardness in the present invention refers to the value that the method based on JIS K-5600 is determined.
In addition, the preferred 1GPa of modulus of elasticity in the physical property of the solidfied material as the composition in the present invention, bend test More than, maximum strain preferably more than 2%.There is the solidfied material of composition the modulus of elasticity then to turn into the solidfied material of excellent rigidity, In addition, then turning into tough solidfied material with the maximum strain.
It should be noted that the modulus of elasticity in bend test in the present invention refers to：With distance between the fulcrum 30mm, curved Qu Sudu 0.2mm/ minutes in the bend test that carries out, is worth as obtained by the Stress calculation of strain 0.1% and 1%.
In addition, the maximum strain in the present invention refers to：Stress shows the strain of maximum in identical experiment.
Preferably 0~250 DEG C of the glass transition temperature (hereinafter referred to as " Tg ") of the solidfied material of composition, more preferably 20~ 230℃.By the way that Tg is set into more than 0 DEG C, resin sheet turns into rigidity, the resin sheet of excellent heat resistance obtained from, by setting For less than 250 DEG C, so as to keep obdurability.
It should be noted that the Tg in the present invention refers to：Surveyed under frequency 1Hz, 2 DEG C/min of warming temperature, stretch mode In fixed dynamic viscoelastic spectrogram, stretching loss factor tan δ reach temperature during maximum.
3-3. thickness
As the thickness of resin sheet, can suitably it be set according to purpose.
Particularly in the case where replacing purposes for glass such as OPS, preferably 100 μm~5mm, more preferably 200 μm~ 3mm, particularly preferred 300 μm~2mm.
4. the manufacture method of resin sheet
As the resin piece making method of the composition using the present invention, various methods can be used.
Specifically, when using active energy ray-curable composition as composition, for example following 4 can be enumerated Plant manufacture method.
1) preparation method 1-1
The coating composition on base material, the method for carrying out active energy beam irradiation and solidifying composition
2) preparation method 1-2
The coating composition on base material, after being fitted with other base materials, and carrying out active energy beam irradiation consolidates composition The method of change
3) preparation method 1-3
Composition is set to flow into the base material with spatial portion, the side for carrying out active energy beam irradiation and solidifying composition Method
4) preparation method 1-4
Composition is flowed into the base material with spatial portion, after being fitted with other base materials, carry out active energy beam irradiation And the method for solidifying composition
In the case of these manufacture methods, it can also be heated after irradiation active energy beam.
When glass will be used for instead of purposes by the resin sheet that the composition of the present invention is obtained, preferably above-mentioned preparation method 1-4.
When using thermohardening type composition as composition, for example following 4 kinds of manufacture methods can be enumerated.
5) preparation method 2-1
The coating composition on base material, the method for heating and solidifying composition
6) preparation method 2-2
The coating composition on base material, after being fitted with other base materials, the method for heating and solidifying composition
7) preparation method 2-3
Composition is set to flow into the base material with spatial portion, the method for heating and solidifying composition
8) preparation method 2-4
Composition is flowed into the base material with spatial portion, after being fitted with other base materials, heat and make what composition solidified Method
When glass will be used for instead of purposes by the resin sheet that the composition of the present invention is obtained, preferably above-mentioned preparation method 2-4.
As polymerization methodses, any of batch-type and continous way can be used.
As the example of continous way, it can enumerate：Coating composition flows into composition, continuous supply banding substrate Method as base material etc..
As another example of continous way, in addition to the foregoing, the method for being referred to as continuous casting process can also be enumerated. I.e., it is possible to method being listed below etc.：The band of 2 continuous mirror face stainless steels is being arranged above and below into track shape, is making composition Flow into the band and between, make band slow mobile while continuously being polymerize in band and between, so as to manufacture resin Piece.
In glass replaces purposes, preferred batch-type.
4-1. base material
As base material, the base material that can peel off and base material (hereinafter referred to as " the non-release property without release property can be used Any of base material ").
As the base material that can be peeled off, it can enumerate：Film after metal, glass, demoulding processing and there is the surface of fissility Untreated film (hereinafter collectively referred to as " Mould release material ") etc..
As Mould release material, it can enumerate：Untreated poly- pair of organosilicon processing polyethylene terephthalate film, surface PET film, the untreated OPP films (polypropylene) of the untreated cyclo-olefin-polymer films in surface and surface etc..
For the obtained resin sheet of composition by the present invention, in order to be set to low haze or in order to assign surface smoothness, As the base material that can be peeled off, the base material that surface roughness (center line average roughness) Ra is less than 0.15 μm is preferably used, More preferably 0.001~0.100 μm of base material.In addition, being used as mist degree, preferably less than 3.0%.
As the specific example of the base material, it can enumerate：Glass, the untreated polyethylene terephthalate in surface Film, the untreated OPP films (polypropylene) in surface etc..
It should be noted that in the present invention, surface roughness Ra refers to the bumps on film surface are measured and calculated It is worth obtained by mean roughness.
As non-release property base material, various plastics other than the above can be enumerated, can be enumerated：Polyvinyl alcohol, triacetyl The cellulose ethanoate such as cellulose and diacetyl cellulose resin, acrylic resin, polyester, makrolon, polyarylate, polyethers Sulfone, using cyclic olefins such as ENBs as cyclic polyolefin resin of monomer etc..
As the base material with spatial portion, the base material with recess can be enumerated.It can be set forth in output in Mould release material and set The base material of recess is formed for the hole of the regulation shape of target film thickness.
In this case, composition is made to flow into after the base material with recess, can also be on the base material that this has recess Overlapping other base materials.
As other examples of the base material with spatial portion, it can enumerate：Weir dike (distance piece) is provided with Mould release material So that solidfied material reaches base material (hereinafter referred to as " mould ") of target film thickness etc..In this case, can also be in Yan Di Upper overlapping other base materials.
It is used as Mould release material in this case, preferably glass and the glass for having carried out demoulding processing.
As the example of mould, enumerate Fig. 1 to illustrate.
Fig. 1 (a1-1) and (a1-2) is by 2 plate substrate (Fig. 1：(a1-1) (1) ' of (1) and (a1-2)), 2 Excellent base material (the Fig. 1 of release property：(a1-1) (2) ' of (2) and (a1-2)) and 1 base material (Fig. 1 for being used to set weir dike： (a1-1) (3)) constitute mould example.
Fig. 1 (a2) is by 2 plate substrate (Fig. 1：(a2) (1) and (1) ') and 1 base material (figure for being used to set weir dike 1：(a2) (3)) constitute mould example.
As shown in figure 1, base material (Fig. 1 for setting weir dike：(a1-1) (3)) preferably have on top for injecting Shape (Fig. 1 of the hollow hole part of composition：(a1-1) (3-1)).As the base material that this is used to set weir dike, it can use each Material is planted, organic silicon rubber etc. can be enumerated.
As the specific example of Fig. 1 (a1-1) and (a1-2), it can enumerate：By 2 sheet glass as base material, 2 The film and 1 mould for setting the base material of weir dike to constitute of demoulding processing are carried out.
In glass (Fig. 1：(a1-1) (1)) on it is overlapping carried out the demoulding processing film (Fig. 1：(a1-1) (2)), It is overlapping thereon to be used to set base material (Fig. 1 of weir dike：(a1-1) (3)) and form weir dike (distance piece).Further, at it Upper overlapping film (Fig. 1 for having carried out demoulding processing：(a1-2) (2) '), in overlapping glass (Fig. 1 thereon：(a1-2) (1) '), so as to form mould.
As the specific example of Fig. 1 (a2), base material (Fig. 1 is being used as using glass, the metal for be stripped processing： (a2) (1) and (1) ') in the case of, the release property of solidfied material is excellent, therefore does not need in Fig. 1 (a1-1), (a1-2) 2 carried out the demoulding processing film.
In addition, when solidfied material the release property of composition in itself is excellent, base material (Fig. 1 can also be used glass as： (a2) (1) and (1) ').As the example that solidfied material the release property of composition in itself is excellent, it can enumerate：Match somebody with somebody in composition Close the example for having releasing agent.
The handle before happening of 4-2. compositions
Be coated or injected into the present invention composition when, in order that resulting resin film turn into prevent foreign matter be mixed into and The generation of the defects such as space or the resin film that optics physical property is excellent are prevented, as composition, preferably uses and stirs material composition Mix, mix after the composition that is purified.
As the purification process of composition, the method filtered to composition is easy, so that it is preferred that.It is used as the side of filtering Method, can enumerate pressure filtration etc..
Filtering accuracy is preferably less than 10 μm, more preferably less than 5 μm.Filtering accuracy is smaller more preferred, if but it is too small, Then filter is easily blocked, the replacement frequency increase of filter, and productivity ratio declines, therefore lower limit is preferably 0.1 μm.
When manufacturing resin sheet, in order to prevent that bubble is included in solidfied material, preferably carried out after each composition is coordinated at deaeration Reason.
The method handled as deaeration, can enumerate and utilize standing, vacuum decompression, centrifugation, cyclone (rotation public affairs Turn blender), the deaeration that carries out of gas-liquid separation membrane, ultrasonic wave, pressure vibration and multi-screw extruder etc..
It 4-3. is coated or injected into
As the coating method on base material during coating composition, suitably set according to purpose, utilization can be enumerated Known bar coater, distributor, scraper, knife type coater, comma coating machine, reverse roll coaters, die coating machine, lip are applied The method that machine, gravure coater and micro gravure coating machine etc. are coated.
When injecting composition to the base material with spatial portion, it can enumerate：Composition is loaded into the injection devices such as syringe Or injection device and the method injected etc..
As thickness now, suitably set according to the target film thickness of above-mentioned resin sheet.
In the case of being particularly used for glass instead of purposes, preferably OPS purposes, preferably 100 μm~5mm, more preferably 200 μm ~3mm, particularly preferred 300 μm~2mm.
4-4. active energy beams irradiate
For composition, active energy beam during use active energy ray-curable composition, Ke Yilie are used as Lift：Ultraviolet, luminous ray, electron beam and X-ray etc., it is preferably ultraviolet from the viewpoint of solidfied material can be turned into thick film Line and luminous ray.
As ultraviolet lamp, it can enumerate：Low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, gold Belong to halide lamp, black light lamp, electrodeless UV lamp, LED etc..
The irradiation condition such as dosage, exposure intensity in active energy beam irradiation according to used composition, base material and Purpose etc. is suitably set.
In such a case, it is possible to be heated after irradiation active energy beam.It is used as the method for the heating, Ke Yilie Act has and aftermentioned same method.
4-5. heating
For composition, as using heating means during thermohardening type composition, it can enumerate：It is dipped in heat and oil etc. Method, the method using hot pressing and method for being kept in temp.-regulating type thermostat in thermal medium bath etc..
The appropriate setting of the conditions such as heating-up temperature during heating composition, base material and purpose etc. used in.Make For heating-up temperature, preferably 40~250 DEG C.Heat time composition and target resin sheet etc. used in suitably set and are Can, it can enumerate more than 3 hours.In view of economy, the upper limit of heat time preferably less than 24 hours.
Furthermore it is also possible to change heating-up temperature according to purpose.For example, can enumerate：Use the different hot polymerization of decomposition temperature Close situation of initiator etc..As specific temperature, it can enumerate for example：Enter line number under 40~80 DEG C or so of lower temperature After the polymerization of hour, method of polymerization of a few hours etc. is carried out under the higher temperatures more than 100 DEG C.
5. the purposes of resin sheet
Optical sheet can be particularly preferably used as by the resin sheet of the composition manufacture of the present invention.
The optical sheet formed by the composition of the present invention can be used for various optical applications.More specifically, it can enumerate： It is one-piece type that polaroid protective film, prismatic lens support membrane and light guiding film of polarization plates etc. are used for liquid crystal display device, contact panel The piece of liquid crystal display device, various functions film (such as hard smear, cosmetic sheet, transparent conductivity piece) and impart surface configuration Piece (for example moth eye (Moth Eye) type antireflection sheet, the piece of textured structure used for solar batteries) substrate, solar-electricity Light resistance (weatherability) pieces of the outdoor uses such as pond, LED illumination organic EL illuminating are with film, flexible electronic technology transparency and heat-proof The purposes such as piece.
The excellent heat resistance of the optical sheet formed by the composition of the present invention, therefore, it is possible to be preferred for manufacturing electrically conducting transparent Property piece.As the composition used in the purposes, from the vacuum film formation that can suppress transparent conductivity body layer when outgassing production From the viewpoint of life, the no-solvent type composition preferably without organic solvent.
In addition, the optical sheet even thick film of the present invention, heat resistance is still excellent and with flexibility, and it is high intensity, because This may be used as OPS transparent conductivity plate substrate, at this point it is possible to be more than 0.5mm and 1.5mm more preferred with thickness Following optical sheet.
The manufacture method of transparent conductivity piece is according to conventional method.
As the metal oxide for forming transparent conductor layer, it can enumerate：Indium oxide, tin oxide, zinc oxide, oxidation Titanium, indium-tin composite oxides, tin-antimony composite oxides, zinc-aluminium composite oxide, indium-zinc composite oxide, titanium-niobium Composite oxides etc..Among these, from the viewpoint of environmental stability, circuit fabrication, preferably indium-tin composite oxides, Indium-zinc composite oxide.
As the method for forming transparent conductor layer, according to conventional method, it can enumerate：Use the optics of the present invention Piece, the method formed using above-mentioned metal oxide using vacuum film formation apparatus by sputtering method etc..
More specifically, it can enumerate：Using above-mentioned metal oxide as target material, after being dehydrated, deaerating, arranged Gas formation vacuum, optical sheet is set to after set point of temperature, the side of transparent conductor layer is formed on optical sheet using sputter equipment Method etc..
Embodiment
Hereinafter, embodiment and comparative example are shown, the present invention is further elaborated with.
In addition, following " part " refers to parts by weight, " % " refers to weight %.
1. 1~embodiment of embodiment 7,1~comparative example of comparative example 3
1) manufacture of composition
(A) shown in table 1 below and table 2~(C) composition is coordinated according to the ratio shown in table 1 below and table 2, entered Mixed using rotation-revolution mixer ((strain) シ Application キ-あ processed わ と り Practice Taros ARE-250) to one step (1800rpm × 4 minute), deaeration (2000rpm × 1 minute).
Table 1
Table 2
It should be noted that the abbreviation meaning in Tables 1 and 2 is as follows.
(A) composition
Zero (A1) composition：Straight-chain alkyl-sub diacrylate
·HDDA：1,6- hexanediyl ester, Osaka Organic Chemical Industry (strain) Viscoat#230 processed
·NDDA：1,9- nonanediol diacrylate, common prosperity society chemistry (strain) LIGHT ACRYLATE 1.9ND-A processed
Zero (A2) composition：Polyoxy alkylidene diacrylate
M-220：Tripropylene glycol diacrylate, East Asia synthesis (strain) ARONIX M-220 processed
M-240：Polyethylene glycol (n ≈ 4) diacrylate, East Asia synthesis (strain) ARONIX M-240 processed
(B) composition
M-309：Trimethylolpropane trimethacrylate, East Asia synthesis (strain) ARONIX M-309 processed
·UAd：The addition reaction product of IPDI and pentaerythritol triacrylate (has in 1 molecule There are the carabamate adducts of 6 acryloyl groups)
DPHA-4EO：4 moles of ethylene oxide addition product (Japaneses of dipentaerythritol：ジペンタエリスリトール The モ Le of エ チ レ Application オ キ サ イ De 4 is paid plus thing) six acrylate
OT-1000：The addition reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate (is referred to as " adduct "), the mixture (62 with tetramethylol methane tetraacrylate (be referred to as " PETeA ")：38 (weight ratios)), East Asia synthesis (strain) ARONIX OT-1000 processed
·DCPA：Dihydroxymethyl tristane diacrylate, common prosperity society chemical (strain) system, Light Acrylate DCP-A
(C) composition
DC-1173：2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, BASFJapan (strain) systems Darocur 1173
2) manufacture of resin sheet
As the mould for manufacturing resin sheet, the shaping mould shown in Fig. 1 (a1-1) and (a1-2) has been used Tool.
Use 2 glass sheets (100mm × 180mm, thickness 2mm), 2 demoulding processing polyethylene terephthalates (PET) film (100mm × 180mm, east beautiful (strain) セ ラ ピ-Le MFA processed) and 1 organosilicon plate (thickness 1.0mm).
In glass plate (Fig. 1 (a1-1)：(1) overlapping demoulding processing PET film (Fig. 1 (a1-1) on)：(2)), at it Upper overlapping organosilicon plate (Fig. 1 (a1-1)：(3) weir dike (distance piece)), is formed.Further, in overlapping demoulding processing thereon PET film (Fig. 1 (a1-2)：(2) '), in (Fig. 1 (a1-2) of superimposed glass panels thereon：(1) ') and mould is made.
By syringe, will be above-mentioned in obtained composition from the hollow hole part (Fig. 1 (a1- of the organosilicon plate of profiled sheeting 1)：(3-1)) fluid injection.
To obtained mould, visible LED is irradiated from the one side of glass plate side, so that composition solidifies.Irradiation Condition is as shown below.
Zero UV-LED
Utilize オ プ Us-De (strain) LED illumination device processed (365nm exposure intensity 3.6mW/cm2) only from mould Side glass plate side irradiate 60 minutes.
After natural cooling, glass is removed from mould, demoulding processing PET film is peeled off, so as to take out solidfied material.Will be solid The heat treatment of compound progress 6 hours at 150 DEG C in stream of nitrogen gas, so as to obtain resin sheet.
For obtained resin sheet, plastic hardness, pencil hardness and flexural property are evaluated by the following method.These are tied Fruit is shown in Tables 1 and 2.
3) evaluation method
(1) plastic hardness
Using micro Vickers hardness meter (Fischer Instruments company system Fischer scope H100CS), Vickers is used Pressure head is measured with defined press-in condition (0~300mN/10sec → holding 5sec → 300~0mN/10sec), obtains modeling Property hardness (HUpl values).
(2) pencil hardness
It is measured based on JIS K-5600.
(3) flexural property
Resin sheet is cut into the size of length 50 (mm) × width 10 (mm) × thickness 1 (mm), section is put down with sand paper After cunningization, as test film.Bend test is divided using INSTRON5566A in distance between the fulcrum 30mm, rate of bending 0.2mm/ Clock, carry out at 23 DEG C.The modulus of elasticity in static bending (GPa) is calculated by the stress of strain 0.1% and 1%.
2. brief summary
For the composition of 1~embodiment of embodiment 8, the hardness and flexural property of obtained resin sheet are excellent.
On the other hand, the composition of 1~comparative example of comparative example 6 be the composition without (A) composition, it is impossible to take into account hardness and Flexural property.
Industrial applicability
The composition of the present invention can be preferred for the manufacture of resin sheet, and resulting resin sheet can be used for various use On the way, optical sheet can be preferably used as.The optical sheet can have the manufacture for being preferred for transparent conductivity piece, be more preferably used for touch surface The manufacture of plate transparent conductivity piece.

Claims (14)

1. a kind of resin sheet manufacture curing composition, it contains following (A) and (B) compositions, in the conjunction of (A) and (B) composition Measure in 100 weight %, containing the weight % of (A) composition 5~70 and the weight % of (B) composition 95~30,
(A) composition：More than a kind in following (A1) compositions and (A2) composition,
(A1) composition；Two (methyl) acrylate of straight-chain or branched alkylidene with carbon number 4~20,
(A2) composition；PAG two (methyl) acrylate for adding up to 4~20 of the carbon number of polyoxy alkylidene is constituted,
(B) composition：The compound with ethylenically unsaturated group in addition to (A) composition.
2. resin sheet manufacture curing composition according to claim 1, wherein, (A1) composition is selected from Isosorbide-5-Nitrae-fourth Glycol two (methyl) acrylate, 1,6- hexylene glycols two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate With more than a kind in neopentyl glycol two (methyl) acrylate.
3. the resin sheet manufacture curing composition according to claim 1 or claim 2, wherein, (A2) composition is Selected from polyethylene glycol two (methyl) acrylate, (methyl) acrylate of polypropylene glycol two and polytetramethylene glycol two (methyl) acrylic acid More than a kind in ester.
4. the resin sheet manufacture curing composition according to any one of 1~claim 3 of claim, wherein, (B) Composition contains the compound with more than 3 (methyl) acryloyl groups.
5. resin sheet manufacture curing composition according to claim 4, wherein, (B) composition is：It is used as organic polyisocyanate The reaction product of cyanate and hydroxyl (methyl) acrylate and the compound with more than 3 (methyl) acryloyl groups.
6. resin sheet manufacture curing composition according to claim 5, wherein, for (B) composition, at (A) In the weight % of total amount 100 of (B) composition, contained using more than 20 weight % ratio as organic multiple isocyanate with containing hydroxyl The reaction product of base (methyl) acrylate and the compound with more than 3 (methyl) acryloyl groups.
7. the resin sheet manufacture curing composition according to any one of 1~claim 6 of claim, wherein, also Contain Photoepolymerizationinitiater initiater (C).
8. the resin sheet manufacture curing composition according to any one of 1~claim 7 of claim, wherein, also Contain thermal polymerization (D).
9. the resin sheet manufacture curing composition according to any one of 1~claim 8 of claim, wherein, Gu The pencil hardness of compound is more than 3H.
10. a kind of resin sheet, it contains the solidfied material of the composition any one of 1~claim 9 of claim.
11. resin sheet according to claim 10, wherein, the thickness of solidfied material is 100 μm~5mm.
12. a kind of manufacture method of resin sheet, make the composition any one of 1~claim 9 of claim flow into by Base material/and for setting in the mould that base material/base material of weir dike is constituted, then penetrated from arbitrary substrate side irradiation active-energy Line.
13. the manufacture method of resin sheet according to claim 12, wherein, added after irradiation active energy beam Heat.
14. a kind of manufacture method of resin sheet, make the composition any one of 1~claim 9 of claim flow into by Base material/and for setting in the mould that base material/base material of weir dike is constituted, then heated.
CN201580069101.7A 2014-12-19 2015-12-17 Resin sheet manufacture curing composition Pending CN107207643A (en)

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