CN107406690A - Resin composite for forming hard coat layer and its solidfied material - Google Patents

Resin composite for forming hard coat layer and its solidfied material Download PDF

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Publication number
CN107406690A
CN107406690A CN201680011522.9A CN201680011522A CN107406690A CN 107406690 A CN107406690 A CN 107406690A CN 201680011522 A CN201680011522 A CN 201680011522A CN 107406690 A CN107406690 A CN 107406690A
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methyl
compound
weight
acrylate
coat layer
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CN107406690B (en
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江川智哉
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Daicel Corp
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Daicel Chemical Industries Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

The resin composite for forming hard coat layer for the solidfied material that the appearance that offer of the invention can obtain crimpiness is inhibited and has higher case hardness and marresistance.The resin composite for forming hard coat layer of the present invention contains：Multifunctional alicyclic ring epoxy compound (A), multifunctional (methyl) acyclic compound (B), surface modification inorganic particle (C), light cationic polymerization initiator (D) and optical free radical polymerization initiator (E), and the content of above-mentioned (A) is (A) and 3~35 weight % of the content sum (100 weight %) of (B).

Description

Resin composite for forming hard coat layer and its solidfied material
Technical field
The present invention relates to resin composite for forming hard coat layer and its solidfied material.Moreover, it relates to using above-mentioned hard The painting object that coating formation is obtained with resin combination.This application claims the spy to be filed an application on April 21st, 2015 in Japan It is willing to the priority of No. 2015-086412, and its content is incorporated herein.
Background technology
Diaphragm is fitted with the liquid crystal displays such as display, organic el display, plasma scope in liquid crystal, Thus, can obtain prevents picture to be damaged, picture is not easy to adhere to fingerprint, easily wiped the effect for the dirt for being attached to picture. The surface of said protection film is formed with the hard conating for assigning marresistance.Then, in recent years, with raising liquid crystal protective film The requirement of case hardness increase, it is desirable to improve the performance of hard conating.
What is be widely adopted as the method for the case hardness for improving hard conating is the curability chemical combination to form hard conating The curability group of thing it is multiple functionalized.However, for it have passed through multiple functionalized curability compound, it is known that before curing Increase, the i.e. cure shrinkage of resin density can occur afterwards.Then, have that to occur multiple functionalized then cure shrinkage more notable, The problem of causing diaphragm to show crimpiness.
In addition, as improve hard conating marresistance method, it is known in curability compound coordinate aluminum oxide, The method of the inorganic particulates such as silica, titanium oxide, so-called method (the patent text for being referred to as so-called hybrid inorganic-organic Offer 1).
However, in the case of making film making inorganic particulate be dispersed in resin, may be from the film after solidification (cured coating film) observes phenomena such as defect or the increasing of mist degree, brittle generation of inorganic particulate.This is considered as by organic Caused by the compatibility of thing and inorganic matter is bad.Then, the method as the compatibility for improving organic matter and inorganic matter, it is known that There is the method (patent document 2) for making the particle diameter of inorganic particulate reduce the Nano filling formed to nanoscale.However, make In the case of with the inorganic particulate by nanoscale, dispersion stabilization can be caused to reduce, inorganic particulate is easy to each other Condense, it is difficult to keep the transparency of cured coating film.Entered it is also known that having using the shell to inorganic particulate with organic matter The method (patent document 3) for the surface modification inorganic filler that row surface modification forms.However, carried out having used with organic matter In the case of the inorganic particulate of surface modification, the case hardness for improving cured coating film can be caused to become difficult, can be led on the contrary sometimes Case hardness is caused to reduce.
Prior art literature
Patent document
Patent document 1：Japanese Patent Publication 2-60696 publications
Patent document 2：Japanese Unexamined Patent Publication 2005-76005 publications
Patent document 3：Japanese Unexamined Patent Publication 2003-34761 publications
The content of the invention
Problems to be solved by the invention
Therefore, it is inhibited it is an object of the invention to provide the appearance that can obtain crimpiness and there is higher table The resin composite for forming hard coat layer of surface hardness and the solidfied material of marresistance.
It should be noted that " crimpiness " refers to causing when forming film (cured coating film) of solidfied material on base material In the characteristic that base material crimps, " the low crimpiness " again refers to not be easily caused the characteristic crimped in base material.
The method solved the problems, such as
The present inventor has made intensive studies to solve the above problems, and as a result finds, for being contained with specific ratio There are multifunctional cycloaliphatic epoxy, multifunctional (methyl) acyclic compound and have and above-mentioned multifunctional ester ring type (methyl) acryloyl group of the epoxy radicals of epoxide and/or multifunctional (methyl) acyclic compound has the official of reactivity The resin combination for the inorganic particulate that can be rolled into a ball, when irradiating active energy beam, the appearance that can obtain crimpiness is inhibited, i.e. Low crimpiness (or low cure shrinkage), and the solidfied material with higher case hardness and marresistance.The present invention is exactly Completed based on these understanding.
That is, the present invention provides a kind of resin composite for forming hard coat layer, and it contains：There is alicyclic structure in 1 intramolecular Multifunctional alicyclic ring epoxy compound (A) with more than 2 epoxy radicals, in 1 intramolecular there is more than 2 (methyl) acryloyl groups Multifunctional (methyl) acyclic compound (B), the inorganic grain in average grain diameter (being based on dynamic light scattering method) for 0.1~100nm The surface of son has surface modification inorganic particle (C), the light with epoxy radicals and/or the reactive functional groups of (methyl) acryloyl group Cationic polymerization initiators (D) and optical free radical polymerization initiator (E), and the content of above-mentioned (A) be (A) and (B) content it 3~35 weight % of (100 weight %).
In addition, the present invention provides above-mentioned resin composite for forming hard coat layer, wherein, relative to above-mentioned (A) and (B) The parts by weight of total content 100, the content of above-mentioned (C) is 5~40 parts by weight.
In addition, the present invention provides above-mentioned resin composite for forming hard coat layer, wherein, hard conating formation resin combination (A) that is included in thing, (B), (C) total amount in the concentration of (methyl) acryloyl group be more than 5.0 mMs/g.
In addition, the present invention provides above-mentioned resin composite for forming hard coat layer, wherein, surface modification inorganic particle (C) In inorganic particulate be silica.
In addition, the present invention provides above-mentioned resin composite for forming hard coat layer, wherein, further contain in said composition With the compound that at least one of is selected from the group with the reactive functional groups of epoxy radicals and/or (methyl) acryloyl group：Silicon It is compound, (methyl) acyclic compound containing perfluoroalkyl, (methyl) acyclic compound containing silicyl, polyether-modified Poly- (methyl) acrylate of (methyl) acyclic compound, Si modification, polyether-modified poly- (methyl) acrylate, containing perfluoroalkyl Poly- (methyl) acrylate, polyether-modified (methyl) acrylate, acrylic acid modified polydimethylsiloxanes containing perfluoroalkyl Alkane, polyether-modified dimethyl silicone polymer, the dimethyl silicone polymer containing perfluoroalkyl and polyether-modified gathering containing perfluoroalkyl Dimethyl siloxane.
In addition, the present invention provides the solidfied material of above-mentioned resin composite for forming hard coat layer.
In addition, the present invention provides the solidfied material shape possessed on the surface of article by above-mentioned resin composite for forming hard coat layer Into hard conating painting object.
That is, the present invention relates to herein below.
[1] resin composite for forming hard coat layer, it contains：There is alicyclic structure and more than 2 epoxy radicals in 1 intramolecular Multifunctional alicyclic ring epoxy compound (A), there is in 1 intramolecular multifunctional (methyl) third of more than 2 (methyl) acryloyl groups Olefin(e) acid compound (B), average grain diameter (being based on dynamic light scattering method) be 0.1~100nm inorganic particulate surface have with Surface modification inorganic particle (C), the light cationic polymerization of the reactive functional groups of epoxy radicals and/or (methyl) acryloyl group trigger Agent (D) and optical free radical polymerization initiator (E), and the content of above-mentioned (A) is (A) and (B) content sum (100 weight %) 3~35 weight %.
[2] resin composite for forming hard coat layer described in above-mentioned [1], wherein, (A) is the compound (fat shown in formula (I) Ring type epoxide).
[3] resin composite for forming hard coat layer described in above-mentioned [1], wherein, (A) is at least one of is selected from the group Compound：(3,4,3 ', 4 '-diepoxy) connection hexamethylene, double (3,4- epoxycyclohexyl-methyls) ethers, 1,2- epoxies -1,2- it is double (3, 4- 7-oxa-bicyclo[4.1.0-1- bases) ethane, double (3,4- 7-oxa-bicyclo[4.1.0-1- bases) propane of 2,2-, 1,2- it is double (3,4- 7-oxa-bicyclo[4.1.0s- 1- yls) ethane and the compound shown in formula (I-1)~(I-10).
[4] resin composite for forming hard coat layer described in above-mentioned [1], wherein, (A) is 3,4- epoxycyclohexyl-methyls (3,4- epoxies) cyclohexane carboxylate and/or (3,4,3 ', 4 '-diepoxy) connection hexamethylene.
[5] resin composite for forming hard coat layer any one of above-mentioned [1]~[4], wherein, (B) is with 3 More than (such as 3~12, preferably more than 5, particularly preferred 5~10) (methyl) acryloyl group compound.
[6] resin composite for forming hard coat layer any one of above-mentioned [1]~[5], wherein, the molecular weight of (B) For 300~13000.
[7] resin composite for forming hard coat layer any one of above-mentioned [1]~[6], wherein, (B's) divides equally again Son amount (being converted based on GPC, polystyrene standard) is 400~13000.
[8] resin composite for forming hard coat layer any one of above-mentioned [1]~[7], wherein, (B) was two seasons penta Poly- (methyl) acrylate of tetrol or derivatives thereof.
[9] resin composite for forming hard coat layer any one of above-mentioned [1]~[8], wherein, it is inorganic in (C) Particle is silica, titanium dioxide, aluminum oxide or zirconium oxide.
[10] resin composite for forming hard coat layer any one of above-mentioned [1]~[8], wherein, it is inorganic in (C) Particle is silica.
[11] resin composite for forming hard coat layer any one of above-mentioned [1]~[10], wherein, the nothing in (C) The average grain diameter (being based on dynamic light scattering method) of machine particle is 1~10nm.
[12] resin composite for forming hard coat layer any one of above-mentioned [1]~[11], wherein, in (C) with The reactive functional groups of epoxy radicals and/or (methyl) acryloyl group are (excellent selected from hydroxyl, glycidyl ether, alicyclic epoxy group Elect cyclohexene oxide base as) in group.
[13] resin composite for forming hard coat layer any one of above-mentioned [1]~[12], it is further comprising tool Have and be selected from the reactive functional groups of epoxy radicals and/or (methyl) acryloyl group：Silicon compound, (methyl) containing perfluoroalkyl Acyclic compound, (methyl) acyclic compound containing silicyl, polyether-modified (methyl) acyclic compound, Si modification Poly- (methyl) acrylate, polyether-modified poly- (methyl) acrylate, poly- (methyl) acrylate containing perfluoroalkyl, containing perfluor Polyether-modified (methyl) acrylate of alkyl, acrylic acid modified dimethyl silicone polymer, polyether-modified dimethyl silicone polymer, At least one of dimethyl silicone polymer and the polyether-modified dimethyl silicone polymer containing perfluoroalkyl containing perfluoroalkyl are changed Compound.
[14] resin composite for forming hard coat layer any one of above-mentioned [1]~[12], it further contains Poly- (methyl) acrylate of Si modification of hydroxyl.
[15] resin composite for forming hard coat layer any one of above-mentioned [1]~[14], wherein, the content of (A) For 3~50 weight % of the nonvolatile component total amount included in resin combination.
[16] resin composite for forming hard coat layer any one of above-mentioned [1]~[15], wherein, the content of (B) For 40~95 weight % of the nonvolatile component total amount included in resin combination.
[17] resin composite for forming hard coat layer any one of above-mentioned [1]~[16], wherein, hard conating is formed With included in resin combination (A), (B), (C) total amount in (methyl) acryloyl group concentration be more than 5.0 mMs/ g、。
[18] resin composite for forming hard coat layer any one of above-mentioned [1]~[17], wherein, the content of (C) For 1~30 weight % of the nonvolatile component total amount included in resin combination.
[19] resin composite for forming hard coat layer any one of above-mentioned [1]~[18], wherein, relative to above-mentioned (A) with the parts by weight of total content 100 of (B), the content of (C) is 5~40 parts by weight.
[20] resin composite for forming hard coat layer any one of above-mentioned [1]~[19], wherein, (A) and (C) Content sum be (A), (B), (C) summation (100 weight %) 5~60 weight %.
[21] resin composite for forming hard coat layer any one of above-mentioned [1]~[20], wherein, relative to resin Cation-curable compound (particularly multifunctional alicyclic ring epoxy compound (A)) 100 parts by weight included in composition, (D) Content be 1~10 parts by weight.
[22] resin composite for forming hard coat layer any one of above-mentioned [1]~[21], wherein, relative to resin Radically curing compound (particularly multifunctional (methyl) acyclic compound (B)) 100 parts by weight included in composition, (E) content is 1~10 parts by weight.
[23] resin composite for forming hard coat layer any one of above-mentioned [1]~[22], wherein, relative to (A), (B), the summation (100 parts by weight) of (C), have and be selected from the reactive functional groups of epoxy radicals and/or (methyl) acryloyl group Silicon compound, (methyl) acyclic compound containing perfluoroalkyl, (methyl) acyclic compound, polyethers containing silicyl change Property (methyl) acyclic compound, poly- (methyl) acrylate of Si modification, polyether-modified poly- (methyl) acrylate, alkane containing perfluor Poly- (methyl) acrylate of base, polyether-modified (methyl) acrylate, acrylic acid modified poly dimethyl silicon containing perfluoroalkyl Oxygen alkane, polyether-modified dimethyl silicone polymer, the dimethyl silicone polymer containing perfluoroalkyl and polyether-modified containing perfluoroalkyl The content of at least one of dimethyl silicone polymer compound [particularly poly- (methyl) acrylate of Si modification of hydroxyl] For 0.01~10 parts by weight.
[24] solidfied material of the resin composite for forming hard coat layer any one of above-mentioned [1]~[23].
[25] possess on the surface of article as the resin composite for forming hard coat layer any one of [1]~[23] The painting object for the hard conating that solidfied material is formed.
[26] by the way that the resin composite for forming hard coat layer any one of [1]~[23] to be coated on to the table of article Face simultaneously makes painting object obtained from its solidification.
The effect of invention
The resin composite for forming hard coat layer of the present invention, therefore can be by irradiating active-energy due to above-mentioned composition Ray and formed with high surface hardness, excellent scratch resistance and with the solidfied material of low crimpiness (or low cure shrinkage), It can suitably be used as and be used to be formed in plastic films such as TAC (cellulose triacetate), PET (polyethylene terephthalate) The resin combination of hard conating uses.In addition, the resin composite for forming hard coat layer of the present invention can also be preferably as glass The resin composite for forming hard coat layer of base material uses, and in the case of for the purposes, can assign high table having given play to Surface hardness, excellent marresistance effect while also given play to the rupture of glass baseplate and prevent effect.
Brief description of the drawings
[Fig. 1] is used for the sketch illustrated to the crimpiness evaluation method in embodiment.
Embodiment
The resin composite for forming hard coat layer (hereinafter also referred to " resin combination ") of the present invention contains multifunctional alicyclic ring Epoxide (A) and multifunctional (methyl) acyclic compound (B).It should be noted that in this manual, " (methyl) Acrylic acid " represents acrylic acid and/or methacrylic acid (in acrylic acid and methacrylic acid any one or both), on (methyl) acrylate etc. is similarly.
[multifunctional alicyclic ring epoxy compound (A)]
Multifunctional alicyclic ring epoxy compound (A) is that have alicyclic structure and the cation of more than 2 epoxy radicals in 1 intramolecular Curability compound.In the resin combination of the present invention, multifunctional alicyclic ring epoxy compound (A) can be used alone, Or it is used in combination of two or more.
As multifunctional alicyclic ring epoxy compound (A), can specifically enumerate：
(i) there is the change of the epoxy radicals (alicyclic epoxy group) formed by adjacent 2 carbon atoms and oxygen atom for forming alicyclic ring Compound；
(ii) have directly with singly bound in the compound of the epoxy radicals of alicyclic ring；
(iii) there is the compound of alicyclic ring and glycidyl；Etc..
There is the compound of alicyclic epoxy group as above-mentioned (i), can enumerate for example：Compound shown in following formula (I)s (cycloaliphatic epoxy).
[chemical formula 1]
In above-mentioned formula (I), X represents singly-bound or links group (divalent group with more than 1 atom).As above-mentioned company Group is tied, can be enumerated for example：Bivalent hydrocarbon radical, carbon-to-carbon double bond partly or entirely have passed through epoxidised alkenylene, carbonyl, ether Key, ester bond, carbonate group, amide groups, by multiple groups to link in these groups etc..It should be noted that form More than 1 of the carbon atom of cyclohexane ring (cyclohexene oxide base) in formula (I) can also be bonded with substituents such as alkyl.
As above-mentioned bivalent hydrocarbon radical, carbon number can be enumerated as 1~18 straight-chain or alkylidene, the divalence fat of branched Ring type alkyl etc..As the straight-chain or the alkylidene of branched that carbon number is 1~18, can enumerate for example：Methylene, methyl Methylene, dimethylated methylene base, ethylidene, propylidene, trimethylene etc..As above-mentioned divalence alicyclic type hydrocarbon, example can be enumerated Such as：1,2- cyclopentylenes, 1,3- cyclopentylenes, cyclopentylidene, 1,2- cyclohexylidenes, 1,3- cyclohexylidenes, 1,4- cyclohexylidenes, ring Cycloalkylidenes such as oneself fork (including cycloalkanes fork) etc..
Epoxidised alkenylene (also referred to as " epoxidation Asia alkene is partly or entirely have passed through as above-mentioned carbon-to-carbon double bond Base ") in alkenylene, can enumerate for example：Ethenylidene, allylidene, 1- butenylidenes, 2- butenylidenes, Aden's dialkylene, The straight-chain of the carbon numbers 2~8 such as inferior pentenyl, sub- hexenyl, sub- heptenyl, sub- octenyl or the alkenylene of branched etc.. Particularly, epoxidised alkenylene is have passed through as above-mentioned epoxidation alkenylene, the whole of preferably carbon-to-carbon double bond, more preferably The alkenylene of epoxidised carbon number 2~4 is have passed through for the whole of carbon-to-carbon double bond.
As the link group in above-mentioned X, the link group particularly preferably containing oxygen atom, can specifically enumerate：- CO- ,-O-CO-O- ,-COO- ,-O- ,-CONH-, epoxidation alkenylene；By multiple groups to link in these groups； By 1 in these groups or more than 2 and 1 or more than 2 group to link in above-mentioned bivalent hydrocarbon radical etc..
As the typical example of the compound shown in above-mentioned formula (I), can enumerate：(3,4,3 ', 4 '-diepoxy) connection hexamethylene, Double (3,4- 7-oxa-bicyclo[4.1.0-1- bases) ethane of double (3,4- epoxycyclohexyl-methyls) ethers, 1,2- epoxies-1,2-, the double (3,4- of 2,2- 7-oxa-bicyclo[4.1.0-1- bases) propane, double (3,4- 7-oxa-bicyclo[4.1.0-1- bases) ethane of 1,2- or following formula (I-1)~(I-10) institute Compound shown etc..L in following formula (I-5) is the alkylidene of carbon number 1~8, wherein preferably methylene, ethylidene, The straight-chain of the carbon numbers such as propylidene, isopropylidene 1~3 or the alkylidene of branched.Following formula (I-5), (I-7), (I- 9), the n in (I-10)1~n81~30 integer is represented respectively.
[chemical formula 2]
[chemical formula 3]
There is the compound of alicyclic epoxy group as (i), can be used for example：Trade name " CELLOXIDE2021P ", " the commercially available product such as CELLOXIDE 2081 " (above by (strain) Daicel systems).
Have as above-mentioned (ii) directly with the compound of epoxy radicals of the singly bound in alicyclic ring, can enumerate for example：It is following Compound shown in formula (II) etc..
[chemical formula 4]
In formula (II), R' is that the group (organic group of p valencys that p hydroxyl (- OH) forms is removed from the structural formula of p member alcohol Group), p, n represent natural number respectively.As p members alcohol [R'- (OH)p], it is polynary that double (the hydroxymethyl)-n-butyl alcohols of 2,2- etc. can be enumerated Alcohol (alcohol of carbon number 1~15 etc.) etc..P is preferably that 1~6, n is preferably 1~30.In the case that p is more than 2, respective side The n in group in bracket (bracket in outside) can be the same or different.As the compound shown in above-mentioned formula (II), tool Body can enumerate 1,2- epoxies -4- (2- epoxy ethyls) hexamethylene addition product of double (the hydroxymethyl)-n-butyl alcohols of 2,2- [for example, business Name of an article " EHPE3150 " ((strain) Daicel systems) etc.] etc..
There is the compound of alicyclic ring and glycidyl as above-mentioned (iii), can enumerate for example：Bisphenol type epoxy chemical combination The hydrogenated compound (hydrogenated bisphenol A type epoxide) formed of thing, the hydrogenated chemical combination formed of bisphenol F type epoxy compound Thing (A Hydrogenated Bisphenol A F type rings oxygen compound), A Hydrogenated Bisphenol A type ring oxygen compound, hydrogenation phenol novolak-type epoxy compound, Hydrogenate cresol novolak type epoxy compound, the hydrogenation cresol novolak type epoxy compound of bisphenol-A, hydrogenated naphthalene type ring oxygen The hydrogenated aromatic glycidyl ether type epoxies such as compound, the hydrogenated epoxy compound of epoxide obtained by triphenol methane Compound etc..
As multifunctional alicyclic ring epoxy compound (A), from low crimpiness can be obtained and case hardness is high and the transparency Set out in terms of excellent solidfied material, preferably (i) has compound of alicyclic epoxy group, particularly preferably 3,4- epoxy hexamethylenes Ylmethyl (3,4- epoxies) cyclohexane carboxylate [compound, trade name " CELLOXIDE 2021P " shown in above-mentioned formula (I-1) ((strain) Daicel systems) etc.] and (3,4,3', 4'- diepoxy) connection hexamethylene.
(A) content (use level) for the present invention resin combination in include nonvolatile component (beyond solvent into Point) such as 3~50 weight % of total amount, the upper limit is preferably 38 weight %, particularly preferably 33 weight %, is most preferably 29 weights Measure %, especially preferably 25 weight %.Lower limit is preferably 6 weight %, particularly preferably 10 weight %, is most preferably 13 weights Measure %, especially preferably 17 weight %.
In addition, the content (use level) of (A) is 3~35 weight %, excellent of (A) and the content sum (100 weight %) of (B) Elect 10~33 weight %, particularly preferably 13~29 weight % as, be most preferably 17~25 weight %.
By the way that the content of (A) is controlled in above range, can obtain reduces crimpiness while marresistance is kept Effect.(A) when content exceedes above range, the content of multifunctional (methyl) acyclic compound (B) described later tails off, thus Anti- crimpiness occurs, it is difficult to obtain the solidfied material of low crimpiness.It additionally, there are the tendency of marresistance reduction.On the other hand, (A) when content is less than above range, the content of multifunctional (methyl) acyclic compound (B) described later can be caused excessive, because And just crimp occurs, it is difficult to obtain the solidfied material of low crimpiness.
[multifunctional (methyl) acyclic compound (B)]
Multifunctional (methyl) acyclic compound (B) in the present invention is that have more than 2 (methyl) propylene in 1 intramolecular The radically curing compound of acyl group.In the resin combination of the present invention, multifunctional (methyl) acyclic compound (B) can To be used alone a kind of or be used in combination of two or more.
Acryloyl group that the intramolecular of multifunctional (methyl) acyclic compound (B) has and/or methylacryloyl Number (sum) be more than 2, for example, 2~15, more preferably more than 3 (for example, 3~12), be more preferably 5 More than individual (for example, 5~10).
The molecular weight of multifunctional (methyl) acyclic compound (B) is, for example, 300~13000, be preferably 400~13000, Particularly preferably 500~10000, it is most preferably 500~3000.In addition, the weight of multifunctional (methyl) acyclic compound (B) is equal Molecular weight (Mw) is, for example, 400~13000, is preferably 500~10000, is particularly preferably 500~3000.Molecular weight is less than 300 And/or weight average molecular weight be less than 400 when, the crimpiness of solidfied material may be caused to increase.On the other hand, molecular weight and/or weight are equal When molecular weight is more than 13000, the case hardness of solidfied material may be caused to reduce, face coat as diaphragm can not have been given play to The effect of (particularly hard conating).It should be noted that weight average molecular weight is the polystyrene standard conversion using GPC method measure Molecular weight.
As multifunctional (methyl) acyclic compound (B), can enumerate for example：Aliphatic (methyl) acrylate (straight chain Shape or branched aliphatic (methyl) acrylate), non-aromatic (methyl) acrylic acid such as ester ring type (methyl) acrylate Ester)；Aromatic series (methyl) acrylate etc..In the present invention, wherein from the viewpoint of the non-staining of solidfied material, it is preferably Non-aromatic (methyl) acrylate, particularly preferably aliphatic (methyl) acrylate.
Specifically, as multifunctional (methyl) acyclic compound (B), can enumerate for example：2- hydroxyls -3- (methyl) third Alkene acryloxypropylethoxysilane (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, glycerine two (methyl) acrylic acid Ester, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, Tetraethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, DPG two (methyl) acrylate, new penta Glycol two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1, Double [4- (2- (methyl) acryloyls of 9- nonanediols two (methyl) acrylate, 1,10- decanediols two (methyl) acrylate, 9,9- Epoxide ethyoxyl) phenyl] fluorenes, double [4- ((methyl) acryloxy diethoxy) phenyl] propane of 2,2- and their derivative The function of thing etc. two (methyl) acrylate；Ethoxylation isocyanuric acid three (methyl) acrylate, 6-caprolactone are modified three (2- (methyl) acryloyl-oxyethyl) isocyanuric acid ester, glycerine three (methyl) acrylate, ethoxylated glycerol three (methyl) propylene Acid esters, propoxylated glycerol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, trimethylolpropane tris (first Base) acrylate, trimethylolpropane 3 moles of ethylene oxide addition products three (methyl) acrylate, trimethylolpropane Three (methyl) acrylate of 3 mol propylenoxy addition products, trimethylolpropane 6 moles of ethylene oxide addition products three (methyl) acrylate, three (methyl) acrylate of 6 mol propylenoxy addition products of trimethylolpropane, two (three hydroxyl first Base propane) four (methyl) acrylate, ethoxylation pentaerythrite four (methyl) acrylate, pentaerythrite four (methyl) propylene Poly- (methyl) acrylate of acid esters, dipentaerythritol (for example, dipentaerythritol six (methyl) acrylate, dipentaerythritol Six (methyl) acrylate of caprolactone addition product etc.) and they derivative, polyester (methyl) acrylate, polyethers (first Base) acrylate, acrylic acid (methyl) acrylate, carbamate (methyl) acrylate, epoxy (methyl) acrylate, Polydiene (methyl) acrylate (for example, polybutadiene (methyl) acrylate etc.), melamine (methyl) acrylate, Multifunctional (methyl) acrylate more than trifunctionals such as polyacetals (methyl) acrylate etc..
, can be suitably using for example as multifunctional (methyl) acyclic compound (B)：Trade name " DPHA " (Daicel- Allnex (strain) make) etc. commercially available product.
The present invention resin combination in include (A), (B), (C) total amount in (methyl) acryloyl group (for example, more (methyl) acryloyl group that function (methyl) acyclic compound (B) contains) concentration be, for example, be more than 5.0 mMs/g (examples Such as, more than 5.0 mMs/g and be 10.0 mMs/below g), be preferably 5.5 mMs/more than g, more preferably 6.0 mmoles That/more than g, particularly preferably 6.5 mMs/more than g, it is most preferably 7.0 mMs/more than g.It should be noted that (first Base) acryloyl group concentration the upper limit be preferably 9.5 mMs/g, more preferably 9.0 mMs/g, more preferably 8.5 milli Mole/g, particularly preferably 8.0 mMs/g, most preferably 7.5 mMs/g.
(B) nonvolatile component (composition beyond solvent) total amount that content includes in the resin combination for the present invention Such as 40~95 weight %, the upper limit is preferably 90 weight %, more preferably 85 weight %, particularly preferably 80 weight %, optimal Elect 75 weight % as.Lower limit is preferably 45 weight %, more preferably 50 weight %, particularly preferably 55 weight %.
In addition, the content (use level) of (B) be (A) and (B) content sum (100 weight %) 65~97 weight %, Preferably 65~94 weight %, more preferably 65~90 weight %, particularly preferably 65~87 weight %, it is most preferably 68~83 Weight %, especially preferably 73~83 weight %.
By the way that the content of (B) is controlled in above range, can obtain reduces crimpiness while marresistance is kept Effect.(B) when content exceedes above range, the content of foregoing multifunctional alicyclic ring epoxy compound (A) tails off, thus can go out Existing just crimp, it is difficult to obtain the solidfied material of low crimpiness.On the other hand, when the content of (B) is less than above range, foregoing is more The content of function alicyclic ring epoxy compound (A) is excessive, thus anti-crimpiness occurs, it is difficult to obtains the solidfied material of low crimpiness. It additionally, there are the tendency for causing marresistance to reduce.
[surface modification inorganic particle (C)]
Surface modification inorganic particle (C) in the present invention is surface with the ring with multifunctional alicyclic ring epoxy compound (A) The reactive functional groups of epoxide and/or (methyl) acryloyl group (that is, have functional group and (methyl) of reactivity with epoxy radicals Functional group of the acryloyl group with reactivity has reactive functional group with epoxy radicals and (methyl) acryloyl group) nothing Machine particle.Surface modification inorganic particle (C) in the present invention due to above-mentioned reactive functional groups, therefore with the phase of organic matter Capacitive is excellent.In addition, dispersiveness is excellent, it can prevent inorganic particulate from condensing to each other.Wherein, surface in the present invention In the case that modification inorganic particulate (C) has the reactive functional groups with epoxy radicals, meeting and above-mentioned multifunctional alicyclic epoxy chemical combination Thing (A) combines, and surface modification inorganic particle (C) in the present invention has and the reactive functional groups of (methyl) acryloyl group In the case of, it can be combined with above-mentioned multifunctional (methyl) acyclic compound (B), surface modification inorganic particle in the present invention (C), can be with above-mentioned multifunctional alicyclic epoxy in the case of having with the reactive functional groups of epoxy radicals and (methyl) acryloyl group Compound (A) and multifunctional (methyl) acyclic compound (B) combine, therefore lacking for inorganic particulate will not occur from solidfied material Damage, can be that solidfied material assigns excellent marresistance.Further, for solidfied material, additionally it is possible to prevent mist degree increase or Produce fragility.Surface modification inorganic particle (C) can be used alone or be used in combination of two or more.
Above-mentioned inorganic particulate includes the inorganic grain that silica, titanium dioxide, aluminum oxide, zirconium oxide etc. have the transparency Son.In the present invention, wherein in terms of it can suppress the coloring of solidfied material and curability compound (that is, more officials will not be hindered Can alicyclic ring epoxy compound (A), multifunctional (methyl) acyclic compound (B)) solidification, will not also cause above-mentioned curability The aspect that compound and its polymer are decomposed is set out, preferably silica.
The average grain diameter (being based on dynamic light scattering method) of inorganic particulate is 0.1~100nm, is preferably 1~50nm, is especially excellent Elect 3~20nm as.When average grain diameter exceedes above range, the tendency for causing the transparency to reduce be present.On the other hand, average grain diameter During less than above range, the tendency for being difficult to obtain marresistance be present.
As above-mentioned and epoxy radicals and/or the reactive functional groups of (methyl) acryloyl group, can enumerate for example：(methyl) third Enoyl-, glycidyl ether, alicyclic epoxy group, oxetanylmethoxy, vinyl ether group, thia cyclopropyl, vinyl, hydroxyl Deng.In the present invention, wherein from the marresistance aspect that can improve multifunctional alicyclic ring epoxy compound (A), preferably For the reactive excellent group with epoxy radicals, especially preferably hydroxyl, glycidyl ether, alicyclic epoxy group are (for example, oxidation Cyclohexenyl group).
In the present invention, the commercially available product such as trade name " Y10C-MFK " ((strain) Admatechs systems) can suitably be used.
(C) content (use level) for the present invention resin combination in include nonvolatile component (beyond solvent into Point) such as 1~30 weight % of total amount, be preferably 3~25 weight %, particularly preferably 4~20 weight %, be most preferably 5~ 15 weight %.
Relative to the parts by weight of total content 100 of above-mentioned (A) and (B), the content (use level) of (C) is, for example, 5~40 weight Part, be preferably 5~30 parts by weight, more preferably 7~25 parts by weight, particularly preferably 10~20 parts by weight, be most preferably 10~ 15 parts by weight.
In addition, (A) and (C) content sum are above-mentioned (A), (B), (C) summation (100 weight %) such as 5~60 Weight %, the upper limit are preferably 55 weight %, particularly preferably 50 weight %, are most preferably 40 weight %.Lower limit is preferably 10 weights Measure %, particularly preferably 15 weight %, be most preferably 20 weight %, especially preferably 25 weight %.
When containing (C) within the above range, it can obtain having both marresistance, high rigidity, the solidfied material of low crimpiness, from this From the aspect of be preferable.(C) when content is less than above range, the tendency for causing marresistance to reduce be present.On the other hand, (C) when content exceedes above range, the tendency for causing the transparency impaired be present.
Containing surface in the resin combination of the present invention as surface modification inorganic particle (C) has and multifunctional alicyclic ring , can when preparing the resin combination in the case of the inorganic particulate of the reactive functional groups of the epoxy radicals of epoxide (A) With by adding multifunctional alicyclic ring epoxy compound (A) and surface modification inorganic particle (C) respectively and being mixed to prepare, but The tendency for easily producing mist degree be present in the case where the content of surface modification inorganic particle (C) in the composition so obtained. In addition, generally, in the case where surface modification inorganic particle (C) is added into resin combination, to be scattered in the shape in solvent State is added, but substantial amounts of molten due to needing concomitantly to coordinate therewith if more adding surface modification inorganic particle (C) Agent, therefore, in the case where solvent use level is set as into lower value, surface modification inorganic particle (C) can addition be phase When what is be limited.It is therefore preferable that use the reactive functional groups (such as hydroxyl) with epoxy radicals that are making surface modification inorganic particle (C) The material that is formed with the epoxy reaction of multifunctional alicyclic ring epoxy compound (A), by surface modification inorganic particle (C) solvent-free Under be scattered in the material formed in multifunctional alicyclic ring epoxy compound (A) or the surface modification inorganic grain that will be scattered in solvent Sub (C) is mixed with multifunctional alicyclic ring epoxy compound (A) and then is removed the material that solvent forms again.As making multifunctional alicyclic ring ring The material that oxygen compound (A) forms with surface modification inorganic particle (C) reaction, can suitably use such as trade name " NANOPOX C620 " (EVONIC company systems) etc..In addition, as the surface modification inorganic particle for making to have with the reactive functional groups of epoxy radicals (C) material formed in multifunctional alicyclic ring epoxy compound (A) is scattered under solvent-free, can suitably use such as " Y10C- JFS " ((strain) Admatechs systems) etc..
[light cationic polymerization initiator (D)]
Light cationic polymerization initiator is to produce acid, so as to triggering the cation included in resin combination by illumination The compound of the curing reaction of curability compound, it includes the anion of light absorbing cation portion and the occurring source as acid Portion.
As light cationic polymerization initiator, can enumerate for example：DiazoniumSalt compounds, iodineSalt compounds, sulfonium Salt compounds,Salt compounds, selenium salt compounds, oxygenSalt compounds, ammonium salt compounds, bromide class chemical combination Thing etc..
In the present invention, wherein, from the excellent solidfied material aspect of curability can be formed, preferably using sulfonium salt class Compound.As the cation portion of sulfonium salt compounds, can enumerate for example：(4- hydroxy phenyls) methyl-benzyl sulfonium cation, triphen Base sulfonium cation, diphenyl [4- (thiophenyl) phenyl] sulfonium cation, 4- (4- xenyls sulfenyl) phenyl -4- xenyl phenyl sulfoniums from The aryl sulfonium cations such as son, three p-methylphenyl sulfonium cations (particularly triaryl matte ion).
As the anion portion of light cationic polymerization initiator, can enumerate for example：[(Y)sB(Phf)4-s]-(in formula, Y is represented Phenyl or xenyl.Phf represent hydrogen atom at least one by perfluoroalkyl, perfluoro alkoxy and halogen atom extremely Few a kind substitutes the phenyl formed.S be 0~3 integer), BF4 -、[(Rf)tPF6-t]-(in formula, Rf represent hydrogen atom 80% with On the alkyl that is replaced by fluorine atoms.T represent 0~5 integer), AsF6 -、SbF6 -、SbF5OH-Deng.
As the light cationic polymerization initiator in the present invention, can enumerate for example：(4- hydroxy phenyls) methyl-benzyl sulfonium four (pentafluorophenyl group) borate, (pentafluorophenyl group) borate of 4- (4- xenyls sulfenyl) phenyl -4- xenyl phenyl sulfonium four, 4- (benzene Sulfenyl) three (pentafluorophenyl group) borate of phenyl diphenyl sulfonium phenyl, [4- (4- xenyls sulfenyl) phenyl] -4- xenyl phenyl sulfoniums Phenyl three (pentafluorophenyl group) borate, the fluorophosphate of diphenyl [4- (thiophenyl) phenyl] sulfonium three (pentafluoroethyl group) three, diphenyl [4- (thiophenyl) phenyl] sulfonium four (pentafluorophenyl group) borate, diphenyl [4- (thiophenyl) phenyl] sulfonium hexafluorophosphate, 4- (4- Xenyl sulfenyl) three (pentafluoroethyl group) three fluorophosphate of phenyl -4- xenyl phenyl sulfonium, double [4- (diphenyl sulfonium) phenyl] thioethers Phenyl three (pentafluorophenyl group) borate, (phenyl-pentafluoride of [4- (2- thioxanthene ketone groups sulfenyl) phenyl] phenyl -2- thioxanthene ketone group sulfoniums phenyl three Base) borate, 4- (thiophenyl) phenyl diphenyl sulfonium hexafluoro antimonate, trade name " CYRACURE UVI-6970 ", " CYRACURE UVI-6974 ", " CYRACURE UVI-6990 ", " CYRACURE UVI-950 " are (above by U.S. Union Carbide company systems), " Irgacure 250 ", " Irgacure 261 ", " Irgacure 264 " is (above by BASF AG System), " CG-24-61 " (Ciba-Geigy company systems), " Optomer SP-150 ", " Optomer SP-151 ", " Optomer SP-170 ", " Optomer SP-171 " (above by (strain) ADEKA systems), " DAICAT II " ((strain) Daicel systems), " UVAC1590 ", " UVAC1591 " (being made above by Daicel-Cytec (strain)), " CI-2064 ", " CI-2639 ", " CI- 2624 ", " CI-2481 ", " CI-2734 ", " CI-2855 ", " CI-2823 ", " CI-2758 ", " CIT-1682 " are (above by Japan Cao Da (strain) make), " PI-2074 " (Rhodia company systems, four (pentafluorophenyl group) borate toluyl groups cumenyl iodine Salt), " FFC509 " (3M company systems), " BBI-102 ", " BBI-101 ", " BBI-103 ", " MPI-103 ", " TPS-103 ", " MDS-103 ", " DTS-103 ", " NAT-103 ", " NDS-103 " (above by Midori Kagaku (strain) make), " CD-1010 ", " CD-1011 ", " CD-1012 " (above by Sartomer America company systems), " CPI-100P ", " CPI-101A " (more than By SAN-APRO (strain) make) etc. commercially available product.These can be used alone or two or more is applied in combination.
The content of light cationic polymerization initiator (D) in the resin combination of the present invention in resin combination relative to wrapping Cation-curable compound (particularly multifunctional alicyclic ring epoxy compound (A)) 100 parts by weight, for example, 1~10 weight contained Measure part, be preferably 1~5 parts by weight, particularly preferably 2~4 parts by weight.The content of light cationic polymerization initiator (D) is less than upper When stating scope, the hidden danger for causing solidification bad be present.On the other hand, the content of light cationic polymerization initiator (D) exceedes above-mentioned During scope, the tendency that solidfied material easily colours be present.
[optical free radical polymerization initiator (E)]
Optical free radical polymerization initiator be by illumination to produce free radical, so as to trigger included in resin combination from By the compound of the curing reaction of base curability compound, can enumerate for example：Benzophenone, benzyl acetophenone (acetophenone benzyl), benzyl dimethyl ketal, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin are different Propyl ether, dimethoxy-acetophenone, dimethoxyphenylacetophenone, diethoxy acetophenone, Diphenyl disulfide ether, o-benzoyl Yl benzoic acid methyl esters, EDMAB (Japanese chemical drug (strain) system, trade name " KAYACURE EPA " etc.), 2, 4- diethyl thioxanthones (Japanese chemical drug (strain) system, trade name " KAYACURE DETX " etc.), 2- methyl isophthalic acids-[4- (methyl) benzene Base] -2- morpholinoes-acetone -1 (Ciba-Geigy (strain) system, trade name " Irgacure 907 " etc.), 1- hydroxycyclohexylphenyls Ketone (Ciba-Geigy (strain) system, trade name " Irgacure 184 " etc.), 2- dimethylaminos -2- (4- morpholinoes) benzoyl 2- amino -2- benzoyl-the 1- such as base -1- phenyl-propanes phenyl-alkane compounds, four (t-butyl peroxy carbonyl) benzophenone, The amino benzenesulfonamide derivatives such as benzil, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 4,4 '-bis- (diethylamino) benzophenone Thing, 2,2 '-bis- (2- chlorphenyls) -4,5,4 ', 5 '-tetraphenyl -1,2 '-bisglyoxaline (hodogaya chemical (strain) system, trade name " B- CIM " etc.) etc. the halomethylation such as double (trichloromethyl) -4- (4- methoxynaphthalene -1- bases) -1,3,5- triazines of imidazolium compounds, 2,6- Triaizine compounds, 2- trichloromethyls -5- (2- benzofurans -2- bases-vinyl) -1,3,4-The halomethyls such as diazoleDiazole Compound etc..These can be used alone or two or more is applied in combination.
The content of optical free radical polymerization initiator (E) in the resin combination of the present invention is relative in resin combination Comprising radically curing compound (particularly multifunctional (methyl) acyclic compound (B)) 100 parts by weight, for example, 1 ~10 parts by weight, it is preferably 1~5 parts by weight, particularly preferably 1.5~3.5 parts by weight.Optical free radical polymerization initiator (E) When content is less than above range, the hidden danger for causing solidification bad be present.On the other hand, optical free radical polymerization initiator (E) contains When amount exceedes above range, the tendency that solidfied material easily colours be present.
[other curability compounds]
The resin combination of the present invention can also be included except multifunctional alicyclic ring epoxy compound (A), multifunctional (methyl) third Curability compound (also referred to as " other curability compounds ") beyond olefin(e) acid compound (B).As other curability chemical combination Thing, it can enumerate for example：Aromatic glycidyl ether type ring oxygen compound, aliphatic polyol polyglycidyl ether, oxa- ring fourth Hydride compounds (compound with more than 1 oxetanylmethoxy), vinyl ether compound are (with more than 1 vinyl ether group Compound) etc..
In the curability total amount of compound (100 weight %) included in the resin combination of the present invention, multifunctional alicyclic ring ring Ratio shared by oxygen compound (A) and the total content of multifunctional (methyl) acyclic compound (B) is, for example, more than 50 weight %, Preferably more than 70 weight %, it is particularly preferably more than 80 weight %, is most preferably more than 90 weight %.It should be noted that The upper limit of the total content of multifunctional alicyclic ring epoxy compound (A) and multifunctional (methyl) acyclic compound (B) is 100 weights Measure %.The ratio of the total content of multifunctional alicyclic ring epoxy compound (A) and multifunctional (methyl) acyclic compound (B) is less than upper When stating scope, the tendency for being difficult to obtain the solidfied material for having low crimpiness, high surface hardness and excellent marresistance concurrently be present.
[additive]
, can also be in the scope for the effect for not destroying the present invention in the resin combination of the present invention in addition to mentioned component Inside contain various additives.In the present invention, it is excellent wherein from the more excellent solidfied material aspect of marresistance can be obtained Compound of the choosing containing one kind or two or more imparting lubricity.
As the compound for assigning above-mentioned lubricity, can enumerate for example：Silane compound, (methyl) third containing perfluoroalkyl Olefin(e) acid compound, (methyl) acyclic compound containing silicyl, polyether-modified (methyl) acyclic compound, Si modification gather (methyl) acrylate, polyether-modified poly- (methyl) acrylate, poly- (methyl) acrylate, alkane containing perfluor containing perfluoroalkyl Polyether-modified (methyl) acrylate of base, acrylic acid modified dimethyl silicone polymer, polyether-modified dimethyl silicone polymer, contain The dimethyl silicone polymer of perfluoroalkyl, polyether-modified dimethyl silicone polymer containing perfluoroalkyl etc..Above-claimed cpd is preferred With with the reactive functional groups of epoxy radicals and/or (methyl) acryloyl group (can enumerate with surface modification inorganic particle (C) Example identical example).
As above-mentioned silane compound, can enumerate for example：Triethyl silicane, t-butyldimethyl silane etc..
As above-mentioned (methyl) acyclic compound containing perfluoroalkyl, can enumerate for example：2,2,2- trifluoroethyl (first Base) acrylate, the fluoropropyls of 2,2,3,3,3- five (methyl) acrylate, 2- (perfluoro butyl) ethyl (methyl) acrylate, 2- (perfluoro capryl) ethyl (methyl) acrylate etc..
As above-mentioned (methyl) acyclic compound containing silicyl, can enumerate for example：Trimethyl silyl (first Base) acrylate, triisopropylsilyl (methyl) acrylate, three (normal-butyl) silicyl (methyl) acrylate, Tri-iso-butylsilyl (methyl) acrylate, thricyclohexyl silicyl (methyl) acrylate, triphenyl-silyl (methyl) acrylate etc..
Above-mentioned poly- (methyl) acrylate of Si modification is in the end and/or side of poly- (methyl) acrylate as main chain Chain is bonded with the compound of silicon chain (for example, PolydimethylsiloxaneChain Chain).
Above-mentioned polyether-modified poly- (methyl) acrylate be in the end of poly- (methyl) acrylate as main chain and/or Side chain is bonded with the compound of polyether chain.
Above-mentioned poly- (methyl) acrylate containing perfluoroalkyl is in the end of poly- (methyl) acrylate as main chain And/or side chain has the compound of perfluoroalkyl.
Above-mentioned polyether-modified (methyl) acrylate containing perfluoroalkyl is in poly- (methyl) acrylate as main chain End and/or side chain there is the compound of perfluoroalkyl and polyether chain.
Aforesaid propylene acid modified dimethyl polysiloxane is in the end of the dimethyl silicone polymer as main chain and/or side Chain is bonded with the compound of poly- (methyl) acrylic acid chain.
Above-mentioned polyether-modified dimethyl silicone polymer, the dimethyl silicone polymer containing perfluoroalkyl and polyether-modified containing complete The dimethyl silicone polymer of fluoroalkyl, it is and above-mentioned in addition to poly- (methyl) acrylate has been altered to dimethyl silicone polymer It is identical.
As above-mentioned perfluoroalkyl, can enumerate for example：The perfluoroalkyl of the carbon numbers such as perfluoro capryl 3~30.
In the present invention, particularly preferably using the reactivity contained with the epoxy radicals of multifunctional alicyclic ring epoxy compound (A) The compound (for example, poly- (methyl) acrylate of the Si modification of hydroxyl etc.) of especially excellent hydroxyl, hydroxyl value are preferably such as 5 ~150mgKOH/g.
(A), (B), the total amount (100 parts by weight) of (C) included in resin combination relative to the present invention, assigns lubrication Property the addition of compound be, for example, 0.01~10 parts by weight, be preferably (containing being its total amount in the case of of more than two kinds) 0.05~5 parts by weight, particularly preferably 0.1~3 parts by weight.
In addition, solvent (for example, butyl acetate, MEK etc.), polynary can also be used in the resin combination of the present invention Alcohol, auxiliary curing agent, organosilicone compounds, metal oxide particle, rubber particles, defoamer, silane coupler, filling Agent, plasticizer, levelling agent, antistatic additive, releasing agent, surfactant, fire retardant, colouring agent, antioxidant, ultraviolet radiation absorption The usual additives such as agent, ionic adsorption body, fluorophor.The content of these additives is relative to resin combination of the invention (100 weight %), such as can suitably be set in the range of 0~40 weight %, preferably 1~25 weight %.
The resin combination of the present invention can be carried out by by above-mentioned each composition in the state of being heated as needed It is prepared by stirring/mixing.It should be noted that direct use can both be made was advance by each composition for the resin combination of the present invention The composition of the one-pack type of the mixture mixed uses, can also be made for example by be divided into it is more than 2 parts into The multigroup parting for dividing (mixture that each composition can also be two or more composition) to be used after being mixed before use to certainty ratio The composition of (for example, two-component-type) uses.The method of above-mentioned stirring/mixing is not particularly limited, and be can be used and is for example divided at a high speed Dissipate known in various blenders, kneader, roller, ball mill, the rotation-revolution type agitating device such as machine, homogenizer etc. or usual stir Mix/mixed organization.Furthermore it is also possible to carry out deaeration under vacuo after stirring/mixing.
<Hard painting composition>
By making the resin composition of the present invention, low crimpiness can be obtained and case hardness and marresistance are excellent Different solidfied material.Thus, it may be preferable to used using the resin combination of the present invention as hard painting with composition (hard paint).
<Painting object>
By by the present invention resin combination be coated on be used as object (coated object) article [for example, metal or Resin (for example, the plastics such as TAC, PET) base material or film processed etc.] surface and make its solidification, can obtain painting object.With regard to the painting object For, because the curability (curing rate) of the resin combination of the present invention is excellent, and the solidfied material of the present invention is low curling Property and case hardness and excellent scratch resistance, therefore productivity and quality both of which are excellent.
, can be by irradiating ultraviolet or electron beam isoreactivity energy by the resin combination of the present invention after article is coated on Measure ray and solidify in very short time.Light source during as progress ultraviolet irradiation, can be used high-pressure mercury-vapor lamp, high-pressure water Silver-colored lamp, carbon arc lamp, xenon lamp, metal halide lamp etc..Irradiation time according between the species of light source, light source and coated face away from From, other conditions and different, but up to tens of seconds, usually several seconds.Generally usable lamp power output is 80~300W/cm left Right irradiation source.In the case of using electron beam irradiation, preferably using with 50~1000KeV scopes energy electron beam, And exposure is set to be 2~5Mrad.After active energy beam irradiation, (solidify afterwards) can also be heated as needed so as to seek Ask the promotion of solidification.
The resin combination of the present invention can apply to coating agent (particularly hard to apply purposes), ink, bonding agent, sealing Glue, sealant, resist, composite, transparent base, hyaline membrane or piece, optical material (such as optical lens etc.), optics into Type mold materials, electronic material are (for example, Electronic Paper, contact panel, solar cell substrate, fiber waveguide, light guide plate, holographic photograph Phase memory etc.), mechanical part material, electric component material, automotive component material, civil construction material, moulding material, plastics Form the various uses such as material, solvent (for example, reactive diluent etc.).
Embodiment
Hereinafter, the present invention is described in more detail in conjunction with the embodiments, but the present invention is not limited to these implementations Example.
Embodiment 1
[preparation of resin combination]
According to the mixing ratio (unit shown in table:Parts by weight) each composition is mixed, stirred and filled using rotation-revolution type Put (trade name " あ わ と り Practice Taros AR-250 ", (strain) THINKY systems) it is stirred and carries out deaeration, obtain resin group Compound.
[making of cured film]
Gained resin combination is coated on PET base material (trade name " LumirrorT60 ", Toray (strain) using rod coaters System；100 ± 5 μm of thickness) on.Now, it is coated with a manner of dried thickness is reached 20 μm using rod coaters.
Thereafter, after 80 DEG C carry out drying in 1 minute, the state in the closed container that have passed through nitrogen displacement is being added Under, in exposure about 1000mJ/cm2Condition irradiation ultraviolet, thus solidified.
The laminated body (cured film) of the composition with " PET base material/solidfied material (cured coating film) " so obtained is used as Evaluating pencil hardness with and marresistance evaluation sample.
In addition, the laminated body (cured film) from the composition obtained above with " PET base material/solidfied material (cured coating film) " Cut the square test film that the length of side is 10cm.For above-mentioned test film, the numeral 1 entered in Fig. 1 (1a) with circle is determined The thickness of measuring point shown in~5.For above-mentioned whole measuring point, the thickness of PET base material will be subtracted by the thickness of measuring point It is qualified that the thickness of cured coating film obtained from (the good thickness of measured in advance) is considered as in 20 μm ± 2 μm of situation respectively, and by its Used as crimpiness evaluation with sample.For underproof situation, change rod coaters reaches until the thickness of said determination point Untill qualified, repeat above-mentioned coating/dried/cured process, make crimpiness evaluation sample.
Embodiment 2~10, comparative example 1~8
In addition to changing the use level of each composition as shown in Table, implement similarly to Example 1, set Oil/fat composition and its solidfied material (sample).It should be noted that embodiment and comparative example beyond embodiment 1 and comparative example 2 In, carry out solidify afterwards (being heated 2 hours at 80 DEG C) after ultraviolet irradiation.
<Evaluation>
The solidfied material (sample) of resin combination for being obtained in embodiment and comparative example implements following evaluation Experiment.
[pencil hardness]
Cured film (the thickness of cured coating film obtained in embodiment and comparative example is determined using following methods:About 20 μ M) pencil hardness.
The evaluation of the pencil hardness of cured coating film is based on JIS K5600 and carried out.Evaluation is carried out by visual inspection, is used Pencil scrapes the cured coating film in PET base material, and the situation that damage has been confirmed on surface or base material is considered as into NG (bad).Tool For body, repeat to be evaluated first with the pencil of a certain hardness, recycle hardness in the case where not causing damage High 1 grade of pencil carries out evaluating such operation, if it is confirmed that having arrived damage, is then commented again using 1 grade lower than it of hardness Valency.In addition, if it is unconfirmed to damage, then the pencil of the hardness of high 1 rank is reused, is confirming the reproduction of more than 2 times Property in the case of, will not cause damage most hard pencil hardness as the pencil hardness of the cured coating film, evaluation result is with lead The hardness of pen core represents.Appreciation condition is as described below.
Evaluation pencil：Mitsubishi's pencil (strain) makes " pencil hardness test pencil "
Load：750gf
Scratch distance：More than 50mm
Scratch angle：45°
Determination of the environment：23 DEG C, 50%RH
It should be noted that the sample (cured film) for experiment has been used in 23 DEG C, 50%RH constant temperature and humidity machine It has passed through the material after damping in 24 hours.
[crimpiness]
For the sample of the crimpiness evaluation obtained in embodiment and comparative example, determine as shown in Fig. 1 (1b) The warpage of corner in the case of horizontal plane is placed in, and is averaged amount of warpage of the value as cured film.The big sample quilt of amount of warpage Think that cure shrinkage or setting expansion are big.It should be noted that will there occurs cure shrinkage in the case of (cured film and Fig. 1 The face of the horizontal plane contact of (1b) is situation with cured coating film opposite side) warpage be used as on the occasion of, will be swollen there occurs solidifying The warpage of (face contacted with Fig. 1 (1b) horizontal plane of cured film is the situation of cured coating film side) is as negative value in the case of swollen It is shown in table.
[marresistance]
For the cured film (about 20 μm of thickness) obtained in embodiment and comparative example, using #0000 steel wool to applying Surface application is with 500g/cm2Or 1kg/cm2Load carry out 20 reciprocal, 200 reciprocal, 1000 reciprocal frictions, marresistance is carried out Evaluation.It should be noted that the evaluation of marresistance is as described below.
A：By 1000 reciprocal not damageds
B：Microlesion be present by 200 reciprocal not damageds, after 1000 is reciprocal
C：By 200 reciprocal not damageds, minor injury or slight muddy after 1000 is reciprocal be present
D：By 200 reciprocal not damageds, obvious damage or obvious muddy after 1000 is reciprocal be present
E：Microlesion be present by 20 reciprocal not damageds, after 200 is reciprocal
F：By 20 reciprocal not damageds, minor injury or slight muddy after 200 is reciprocal be present
G：By 20 reciprocal not damageds, obvious damage or obvious muddy after 200 is reciprocal be present
H：Microlesion be present after 20 is reciprocal
I：Minor injury or slight muddy after 20 is reciprocal be present
[table 1]
[table 2]
It should be noted that the abbreviation in table 1, table 2 represents following compound.
NANOPOX C620：Make silica (the silica average grain diameter of hydroxyl:10nm) (40 parts by weight) with Compound, trade name " NANOPOX C620 ", EVONIC company systems obtained from CELLOXIDE 2021P (60 parts by weight) reactions
Y10C-JFS：CELLOXIDE 2021P (80.5 parts by weight) and the silica (silica containing alicyclic epoxy group Average grain diameter:10nm) mixture of (19.5 parts by weight), trade name " Y10C-JFS ", (strain) Admatechs systems
CELLOXIDE 2021P：3,4- epoxycyclohexyl-methyls (3,4- epoxies) cyclohexane carboxylate, trade name " CELLOXIDE 2021P ", (strain) Daicel systems
A-9550：Dipentaerythritol polyacrylate, molecular weight:About 554, hydroxyl value:About 56mgKOH/g, Xin Zhong village chemistry (strain) makes
A-TMM-3L-N：Pentaerythritol triacrylate, molecular weight:246th, hydroxyl value:About 112mgKOH/g, Xin Zhong village chemistry (strain) makes
DPHA：Dipentaerythritol acrylate, molecular weight:578th, trade name " DPHA ", Daicel-Allnex (strain) systems
Y10C-MFK：Silica (silica average grain diameter containing glycidyl ether:MEK 10nm) disperses Liquid (silica concentration：30 weight %), trade name " Y10C-MFK ", (strain) Admatechs systems
CPI-210S：The fluorophosphate of diphenyl [4- (thiophenyl) phenyl] sulfonium three (pentafluoroethyl group) three, trade name " CPI- 210S ", SAN-APRO (strain) make
Irgacure 184：1- hydroxycyclohexylphenylketones
BYK-SILCLEAN 3700：The Si modification polyacrylate of hydroxyl, hydroxyl value:About 30mgKOH/g, trade name " BYK-SILCLEAN 3700 ", BYK Chemie Japan (strain) make
Industrial applicibility
By irradiating active energy beam to the resin composite for forming hard coat layer of the present invention, can be formed with high surface Hardness, excellent scratch resistance and the solidfied material with low crimpiness, and the table in plastic foil, glass baseplate can be suitable for Face forms the purposes of hard conating.
Symbol description
1 cured film
2 horizontal planes
3 amount of warpage

Claims (7)

1. resin composite for forming hard coat layer, it contains：
1 intramolecular have alicyclic structure and more than 2 epoxy radicals multifunctional alicyclic ring epoxy compound (A),
1 intramolecular have more than 2 (methyl) acryloyl groups multifunctional (methyl) acyclic compound (B),
Have and epoxy radicals on the surface for the inorganic particulate that the average grain diameter based on dynamic light scattering determination is 0.1~100nm And/or the reactive functional groups of (methyl) acryloyl group surface modification inorganic particle (C),
Light cationic polymerization initiator (D) and
Optical free radical polymerization initiator (E),
The content of (A) is (A) and 3~35 weight % of the content sum (100 weight %) of (B).
2. resin composite for forming hard coat layer according to claim 1, wherein, relative to always containing for (A) and (B) 100 parts by weight are measured, the content of (C) is 5~40 parts by weight.
3. resin composite for forming hard coat layer according to claim 1 or 2, wherein, hard conating formation resin combination (A) that is included in thing, (B), (C) total amount in the concentration of (methyl) acryloyl group be more than 5.0 mMs/g.
4. according to resin composite for forming hard coat layer according to any one of claims 1 to 3, wherein, surface modification inorganic Inorganic particulate in particle (C) is silica.
5. according to resin composite for forming hard coat layer according to any one of claims 1 to 4, it is also containing having and epoxy The reactive functional groups of base and/or (methyl) acryloyl group at least one of are selected from the group compound：
It is silicon compound, (methyl) acyclic compound containing perfluoroalkyl, (methyl) acyclic compound containing silicyl, poly- Ether be modified (methyl) acyclic compound, poly- (methyl) acrylate of Si modification, polyether-modified poly- (methyl) acrylate, containing complete Poly- (methyl) acrylate of fluoroalkyl, polyether-modified (methyl) acrylate, acrylic acid modified poly- diformazan containing perfluoroalkyl Radical siloxane, polyether-modified dimethyl silicone polymer, the dimethyl silicone polymer containing perfluoroalkyl and polyether-modified alkane containing perfluor The dimethyl silicone polymer of base.
6. the solidfied material of resin composite for forming hard coat layer according to any one of claims 1 to 5.
7. possess consolidating by resin composite for forming hard coat layer according to any one of claims 1 to 5 on the surface of article The painting object for the hard conating that compound is formed.
CN201680011522.9A 2015-04-21 2016-04-11 Resin composition for forming hard coat layer and cured product thereof Active CN107406690B (en)

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CN112601724A (en) * 2018-08-22 2021-04-02 住友电气工业株式会社 Optical fiber
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CN112534009A (en) * 2018-08-08 2021-03-19 三菱瓦斯化学株式会社 Hard coating composition, laminate film and cured film
CN112601724A (en) * 2018-08-22 2021-04-02 住友电气工业株式会社 Optical fiber
CN112601724B (en) * 2018-08-22 2022-09-20 住友电气工业株式会社 Optical fiber
US11603331B2 (en) 2018-08-22 2023-03-14 Sumitomo Electric Industries, Ltd. Optical fiber
CN116948523A (en) * 2023-02-03 2023-10-27 北京驳凡科技有限公司 UV resin composition and application thereof
CN116948523B (en) * 2023-02-03 2024-05-03 北京驳凡科技有限公司 UV resin composition and application thereof

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