CN102112306B - Functional panel - Google Patents

Functional panel Download PDF

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Publication number
CN102112306B
CN102112306B CN2009801299643A CN200980129964A CN102112306B CN 102112306 B CN102112306 B CN 102112306B CN 2009801299643 A CN2009801299643 A CN 2009801299643A CN 200980129964 A CN200980129964 A CN 200980129964A CN 102112306 B CN102112306 B CN 102112306B
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methyl
acrylate
monomer
acrylic acid
functional panel
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CN102112306A (en
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石原健延
赤间秀洋
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Bridgestone Corp
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Bridgestone Corp
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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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
    • E04F13/18—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements of organic plastics with or without reinforcements or filling materials or with an outer layer of organic plastics with or without reinforcements or filling materials; plastic tiles
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Architecture (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Finishing Walls (AREA)

Abstract

Provided is a functional panel which can withstand the damage, alteration, discoloration, and dyeing caused by acid-containing detergents or dyeing materials such as hair dyes, which are coming to be used more frequently in recent years. The functional panel is characterized by comprising: a coating layer having a glass transition temperature of 50 DEG C or higher obtained by curing a photocurable resin composition obtained from a photopolymerizable monomer having a solubility parameter (SP value) of 20.0 (J/cm<3>)<0.5> or less and a photopolymerizable oligomer; and a base layer.

Description

Functional panel
Technical field
The Photocurable resin composition that the present invention relates to comprise specific photopolymerization monomer by use improves chemical proofing and anti-chromatic functional panel.
Background technology
As the functional panel of structure material, it is the wall of wall, floor or ceiling as building and the member that configures is given the various functions such as soundproof effect, humidity regulation according to the position of its configuration.When the special member of using in water places such as the bathroom as premises, toilet or kitchens is used, require to have the various characteristicses such as the resistance to water that can tolerate harsher environment for use, moisture-proof.
For example, in patent documentation 1, disclose and further be formed with the decorative panel of filming in the top layer that formed by ultra-violet solidified acrylate resin coating on the bottom coating on the surface that is formed at base material.When using this decorative panel as the member in water as above place, demonstrate excellent hot water resistance, hardness property, solid sense, soil resistance etc., and be difficult to produce and expand, peel off etc.
On the other hand, in recent years, in the wall of premises, particularly bathroom, toilet or kitchen, collaboration has the chance of the coloring agents such as washing agent, hair dye of the strong and stimulating of acid etc. to increase, because these chemical reagent adhere to, not only can produce the rotten, deteriorated of wall, also can cause variable color, dyeing.Undoubtedly rotten, deteriorated is not wish the phenomenon occurred, once and the generation variable color just recovers less than color originally, if dye in addition, along with passage of time also is difficult to all the more return to color originally, this is also the reason of not wishing to occur variable color, dyeing phenomenon.As the functional panel that is disposed at such place, but need the use of wash resistant agent, coloring agent, and do not produce rotten, deteriorated, variable color, dyeing.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 11-20112 communique
Summary of the invention
the problem that invention will solve
Yet, such as disclosed in Patent Document 1, when employing is formed with the functional panel of filming on top layer as the panel under harsher environment for use, for all rotten, deteriorated, variable colors of take that these washing agent, coloring agent etc. are cause and dyeing, might not bring into play sufficient tolerance, the leeway still be improved.
Therefore, rotten, the deteriorated generation that the object of the present invention is to provide the coloring agents such as a kind of washing agent that not only can tolerate the strong and stimulating increased by frequency of utilization in recent years, hair dye to cause, also can tolerate the functional panel of the generation of variable color, dyeing.
for the scheme of dealing with problems
The inventor is in order to address the above problem discovery, by employing use there is specific solubility parameters (SP value) photopolymerization monomer and show the Photocurable resin composition of specific glass transition temperature, can access the also functional panel of excellence of chemical proofing and anti-dyeability, thereby complete the present invention.
That is, functional panel of the present invention, is characterized in that, it comprises: making by solubility parameters (SP value) is 20.0 (J/cm 3) 0.5the Photocurable resin composition that following photopolymerization monomer and optical polymerism oligomer obtain solidifies and forms and glass transition temperature is the coating layer more than 50 ℃; And substrate layer.
In addition, it is desirable to, aforementioned photopolymerization monomer is the monomer shown in following formula (1),
(CH 2＝CR 1COO) nR 2......(1)
(in formula (1), R 1mean hydrogen atom or methyl, R 2the n valency alkyl that means carbon number 5～20.N means 1～4 integer.)
Further, aforementioned photopolymerization monomer is preferably freely (methyl) isobornyl acrylate of choosing, 1, 6-hexylene glycol two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, (methyl) acrylic acid isopentyl ester, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, the different myristin of (methyl) acrylic acid, (methyl) stearyl acrylate base ester, the 3-methyl isophthalic acid, 5-pentanediol two (methyl) acrylate, two (methyl) acrylic acid DOPCP, cyclohexanedimethanol two (methyl) acrylate, (methyl) acrylic acid-1, 9-nonanediol ester, trimethylolpropane tris (methyl) acrylate, at least one monomer in the group that pentaerythrite four (methyl) acrylate forms.
In addition, it is desirable to, the use level of aforementioned photopolymerization monomer and aforementioned optical polymerism oligomer is, is the amount of 70: 30～30: 70 by quality ratio.
Further, the aforementioned substrates layer is preferably by the material that comprises unsaturated polyester resin, filler and glass fibre or carbon fiber and forms.
the effect of invention
The chemical proofing of functional panel of the present invention and anti-dyeability excellence, even and adhere to containing coloring agents such as sour washing agent, hair dyes, can not only fully suppress to go bad, deteriorated, can also fully suppress variable color, dyeing.Therefore, functional panel of the present invention is applicable to being used as the member that the water places such as bathroom, toilet or kitchen of premises are used very much.In addition, not must form other layers such as priming coat, as long as the coating layer formed by specific Photocurable resin composition is set on base material, just can easily realize the functional panel of sufficient chemical proofing and anti-dyeability excellence.
The material that particularly in employing, comprises unsaturated polyester resin, filler and glass fibre or carbon fiber during as base material, can access the functional panel that further keeps good durability on the basis of these characteristics.
The specific embodiment
Below, for the present invention, be elaborated.
Functional panel of the present invention is characterised in that, it comprises: making by solubility parameters (SP value) is 20.0 (J/cm 3) 0.5the Photocurable resin composition that following photopolymerization monomer and optical polymerism oligomer obtain solidifies and forms and glass transition temperature is the coating layer more than 50 ℃; And substrate layer.
[photopolymerization monomer]
Photopolymerization monomer used in above-mentioned Photocurable resin composition is characterised in that, its solubility parameters (SP value) is 20.0 (J/cm 3) 0.5below.This SP value (δ) generally defines by following formula according to molar energy of vaporization (Δ Ev) and the molal volume (V) of liquid.
SP value (δ)=(Δ Ev/V) 0.5
And then, according to the Fedors method, the SP value can be only calculated (with reference to " solubility parameters value (Solubility Parameter Values) ", polymer handbook (Polymer Handbook), the 4th edition editors such as () J.Brandrup) by chemical constitution.In addition, in this manual, the SP value refers to the value of calculating according to the Fedors method, and the lower expression photopolymerization monomer polarity of this value is more weak.The SP value of above-mentioned photopolymerization monomer is preferably 19.6 (J/cm 3) 0.5below, 19.4 (J/cm more preferably 3) 0.5below.Lower limit for the SP value is not particularly limited, and is generally 17.0 (J/cm 3) 0.5above.
If show the photopolymerization monomer of such SP value, can keep the good compatibility with aftermentioned optical polymerism oligomer, effectively reduce the polarity that this monomer self has simultaneously.And, because used photopolymerization monomer is low pole, therefore can infer, when the optical polymerism resin combination that will obtain thus solidifies to form coating layer, the reactivity of the coating layer self after can fully suppressing to solidify.Like this, the functional panel of the present invention that is formed with above-mentioned coating layer not can with unnecessary the reacting of the generations such as cleaning agent, coloring agent, and can show good chemical proofing and anti-dyeability.Particularly in anti-dyeability, bring into play significant effect.
Above-mentioned photopolymerization monomer is preferably used has an above acryloxy (CH 2=CHCOO-) or methacryloxy (CH 2=C (CH 3) COO-) and (methyl) acrylate monomer, can be any one in simple function monomer, difunctionality monomer and multi-functional monomer.
As the simple function monomer, such as listing ester ring type (methyl) acrylate such as (methyl) isobornyl acrylate, (methyl) acrylic acid norbornene ester, (methyl) acrylic acid three ring esters in the last of the ten Heavenly stems, (methyl) acrylic acid two ring pentyl esters, (methyl) acrylic acid two cyclopentene esters, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid-4-butyl cyclohexyl, (methyl) acryloyl morpholine, (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-2-hydroxy butyl ester, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) acrylic acid isopentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid undecyl ester, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate base ester, (methyl) acrylic acid myristin, (methyl) acrylic acid palm ester, (methyl) acrylic acid iso stearyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid butoxyethyl, (methyl) acrylic acid ethyoxyl binaryglycol ester, polyoxyethylene nonylplenyl ether acrylate, (methyl) acrylic acid phenoxy ethyl, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) acrylic acid methoxyl group glycol ester, (methyl) acrylic acid ethoxy ethyl ester, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, 7-amino-3,7-dimethyl octyl group (methyl) acrylate, ether skeleton (methyl) esters of acrylic acid etc.
As the difunctionality monomer, for example can list two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid TEG ester, two (methyl) acrylic acid triglycol ester, 1, 4-butanediol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, two (methyl) acrylic acid DOPCP, three (2-ethoxy) isocyanurate group two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, two (methyl) acrylate of the alkylene oxide addition dihydroxylic alcohols of bisphenol-A, two (methyl) acrylate of the alkylene oxide addition dihydroxylic alcohols of hydrogenated bisphenol A, epoxy (methyl) acrylate that diglycidyl ether addition (methyl) acrylate of bisphenol-A forms etc.
As multi-functional monomer, such as listing trimethylolpropane tris (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, dipentaerythritol monohydroxy five (methyl) acrylate etc.
These photopolymerization monomers can be used separately a kind of, also can be used in combination of two or more.
SP value while in addition, using two or more photopolymerization monomer refers to the value that SP value that various monomers of SP value that this monomer is had have is multiplied by each mixing ratio (take the ratio of monomer total amount as each monomer of 1 o'clock) and these adductions are obtained.For example, with respect to photopolymerization monomer total amount 1, the photopolymerization monomer that the SP value of take is 19.0 as 3/4, the SP value photopolymerization monomer that is 21.0 the amount that is 1/4 is while being coordinated, and obtains the SP value of used photopolymerization monomer integral body according to following formula (X).
The SP value of photopolymerization monomer=(19.0 * 3/4)+(21.0 * 1/4)=19.5... (X)
In above-mentioned photopolymerization monomer, be preferably the monomer shown in following formula (1).
(CH 2＝CR 1COO) nR 2......(1)
In above-mentioned formula (1), R 1mean hydrogen atom or methyl.
In above-mentioned formula (1), R 2the n valency alkyl that means carbon number 5～20, containing hetero atom, can not be also ring-type for chain.In addition, in group-CH 2-can replace by use-CH=CH-.N means 1～4 integer.
That is, in above-mentioned formula (1), for example, in the situation that be chain and for saturated monomer, R during n=1 2for the alkyl of carbon number 5～20, R during n=2 2alkylidene for carbon number 5～20.And then, for chain and while being saturated monomer, R during n=3 2for three of carbon number 5～20 replaces alkyl group (alkane triyl), during n=4, be that four of carbon number 5～20 replace alkyl group (alkane tetrayl).As such R 2, for example have-CH 2cH 3,-CH 2cH 2cH 3,-CH (CH 3) CH 3, the alkyl such as cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl ,-CH 2cH 2-,-CH 2cH 2cH 2-,-CH (CH 3) CH 2-wait alkylidene, three replacement alkyl groups as shown in following formula (2), four replacement alkyl groups as shown in following formula (3) etc.
[Chemical formula 1]
Figure BPA00001308007000071
[Chemical formula 2]
R 2carbon number be less than at 5 o'clock, in the situation that be the alkyl of chain, the SP value of monomer has the tendency of rising, in the situation that be the alkyl of ring-type, obtains the difficulty that itself becomes.In addition, R 2carbon number surpass at 20 o'clock, in the situation that be the alkyl of chain, the glass transition temperature of gained Photocurable resin composition has to reduce and is inclined to, in the situation that be the alkyl of ring-type, the crosslink density of gained Photocurable resin composition has the tendency of reduction.Suppose that crosslink density surpasses when required ground is undue to be reduced, the coloring agents such as hair dye are easy to be penetrated into coating layer inside, so panel likely is colored.
As the monomer shown in above-mentioned formula (1), particularly, can list (methyl) isobornyl acrylate, 1, 6-hexylene glycol two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, (methyl) acrylic acid isopentyl ester, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, the different myristin of (methyl) acrylic acid, (methyl) stearyl acrylate base ester, the 3-methyl isophthalic acid, 5-pentanediol two (methyl) acrylate, two (methyl) acrylic acid DOPCP, cyclohexanedimethanol two (methyl) acrylate, two (methyl) acrylic acid-1, 9-nonanediol ester, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate.Wherein, from improving the viewpoint of glass transition temperature, the monomer that preferably there is cyclic hydrocarbon group, more preferably (methyl) isobornyl acrylate, dihydroxymethyl tristane two (methyl) acrylate.Such monomer, have SP value preferably if, therefore has the tendency that shows good low pole, can further improve chemical proofing and the anti-dyeability of gained functional panel.In addition, also can effectively bring into play the function as the reactive diluent of optical polymerism oligomer described later.
In addition, functional group's number of above-mentioned photopolymerization monomer is generally 1～6, is preferably 1～4.In addition, functional group's number here refers to, obtains the above-mentioned functional group number, these are average of a plurality of molecules, is converted into the value of the functional group's number had in a part.Functional group's number is 1 o'clock, and crosslink density has the tendency of rising, but owing to improving glass transition temperature thereby can access the functional panel that is formed with the good chemical proofing of performance and anti-chromatic coating layer.Now, aspect the raising glass transition temperature, be preferably the photopolymerization monomer with ring-shaped structure.On the other hand, functional group's number is 2～6, is preferably at 2～4 o'clock, therefore have the tendency that can suitably keep the cross-linking reaction of Photocurable composition, can infer, especially being easy to effectively to suppress coloring agent, to be penetrated into coating layer inner and make the phenomenon of panel dyeing.Therefore in this case, the functional panel that is formed with the coating layer with suitable curing property can kept under chemical proofing and the state of anti-the dyeability obtaining effectively.
[optical polymerism oligomer]
As the optical polymerism oligomer used in above-mentioned Photocurable resin composition, particularly, such as listing polyurethane series (methyl) acrylate oligomer, epoxy system (methyl) acrylate oligomer, ether system (methyl) acrylate oligomer, ester system (methyl) acrylate oligomer, polycarbonate-based (methyl) acrylate oligomer, fluorine system (methyl) acrylate oligomer, silicon-type (methyl) acrylate oligomer etc.These optical polymerism oligomer can synthesize as follows: by addition product of (methyl) acrylic acid and polyethylene glycol, polyoxypropylene glycol, polytetramethylene ether diol, bisphenol A type epoxy resin, phenol novolak type epoxy resin, polyalcohol and 6-caprolactone etc., reacted; Perhaps make polyisocyanate compound and (methyl) acrylate compounds with hydroxyl carry out urethane.
Above-mentioned optical polymerism oligomer can be any one in simple function oligomer, Difunctional oligomers, multifunctional oligomer, and the viewpoint from the crosslink density of the appropriateness that realizes the gained Photocurable resin composition, be preferably multifunctional oligomer.
In these optical polymerism oligomer, from giving the viewpoint as the suitable characteristic except chemical proofing and anti-dyeability of functional panel, be preferably polyurethane series (methyl) acrylate oligomer.Polyurethane series (methyl) acrylate oligomer, (methyl) acrylate that for example can carry out the synthesis of polyurethane prepolymer by polyalcohol and polyisocyanates, this polyurethane prepolymer addition is had to a hydroxyl is manufactured, and it can be polyurethane series (methyl) acrylate oligomer with carbonic ester skeleton.
The synthetic middle polyalcohol used of above-mentioned polyurethane prepolymer is for having the compound of a plurality of hydroxyls (OH yl), particularly, can list PPG, PEPA, poly-BDO, polybutadiene polyol, alkylene oxide modified polybutadiene polyalcohol and polyisoprene polyalcohol etc.These polyalcohols can be used separately a kind of, also can be used in combination of two or more.In addition, above-mentioned PPG can obtain by addition polymerization, such as making the polyalcohol additions such as the alkylene oxide such as oxirane, expoxy propane and ethylene glycol, propane diols, glycerine, trimethylolpropane, pentaerythrite, D-sorbite.In addition, also can obtain PPG by ring-opening polymerisation, as such PPG, for example can list the poly-BDO that the ring-opening polymerisation by oxolane (THF) obtains.
Above-mentioned PEPA also can obtain by addition polymerization, for example can be by ethylene glycol, diethylene glycol, 1,4-butanediol, 1, the polyalcohols such as 6-hexylene glycol, propane diols, trimethylolethane, trimethylolpropane, with polybasic carboxylic acids such as adipic acid, glutaric acid, butanedioic acid, decanedioic acid, pimelic acid, suberic acids and obtain.In addition, also can obtain PEPA by ring-opening polymerisation, as such PEPA, can list the lactone that the ring-opening polymerisation by 6-caprolactone obtains is PEPA.
It as above-mentioned polyisocyanates, is the compound with a plurality of NCOs (NCO yl), particularly, can list toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), rough methyl diphenylene diisocyanate (rough MDI), IPDI (IPDI), hydrogenated diphenyl methane diisocyanate, HTDI, hexamethylene diisocyanate (HDI), their isocyanurate-modified thing, Carbodiimide-Modified thing, glycol modification thing etc.These polyisocyanates can be used separately a kind of, also can be used in combination of two or more.
In above-mentioned polyurethane prepolymer synthetic, preferably use urethane reaction catalyst.Use catalyst as this urethane reaction, can list the organo-tin compounds such as dibutyl tin laurate, dibutyltin diacetate, thiocarboxylic acid dibutyl tin, two maleic acid dibutyl tins, thiocarboxylic acid dioctyl tin, octenoic acid tin, monobutyltin oxide; The inorganic tin compounds such as stannous chloride; The organo-lead compounds such as octene lead plumbate; The cyclic amines such as triethylenediamine; The organic sulfonic acids such as p-methyl benzenesulfonic acid, pyrovinic acid, fluosulfonic acid; The inorganic acids such as sulfuric acid, phosphoric acid, perchloric acid; The bases such as sodium alkoxide, lithium hydroxide, aluminium alcoholates (aluminum alcoholate), NaOH; The titanium compounds such as butyl titanate, tetraethyl titanate, tetraisopropyl titanate; Bismuth compound; Quaternary ammonium salt etc.In these catalyst, preferably have machine tin compound.These catalyst can be used separately a kind of, also can be used in combination of two or more.With respect to the above-mentioned polyalcohol of 100 mass parts, the consumption of above-mentioned catalyst is preferably the amount of the scope of 0.001～2.0 mass parts.
In addition, above-mentioned and the polyurethane prepolymer addition, (methyl) that have hydroxyl acrylate is to have an above hydroxyl and have (methyl) acryloxy (CH more than 2=CHCOO-or CH 2=C (CH 3) COO-) and compound.This have hydroxyl (methyl) acrylate can with the NCO addition of above-mentioned polyurethane prepolymer.There is the acrylate of hydroxyl as this, can list acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, pentaerythritol triacrylate etc.These acrylate with hydroxyl can be used separately a kind of, also can be used in combination of two or more.
By the optical polymerism oligomer by such, together with above-mentioned photopolymerization monomer, coordinate, as described later, the glass transition temperature that can optimization gained Photocurable resin composition curing coating layer shows, and can access and can bring into play excellent chemical proofing and anti-chromatic Photocurable resin composition.
[Photocurable resin composition]
The Photocurable resin composition used in functional panel of the present invention contains above-mentioned optical polymerism oligomer and above-mentioned photopolymerization monomer.The use level of these optical polymerism oligomer and photopolymerization monomer by quality ratio for being generally 70: 30～30: 70, be preferably 40: 60～amount of 60: 40.When the use level of monomer is very few, the likely viscosity rise of gained Photocurable resin composition, coating variation, and likely can't give full play to the physical property such as chemical proofing and anti-dyeability.In addition, when the use level of monomer is too much, there is the tendency that flexibility reduces, fragility uprises of filming.Therefore, if the use level of optical polymerism oligomer and photopolymerization monomer is in above-mentioned scope, can give full play to the low pole that photopolymerization monomer has, and the glass transition temperature of the coating layer after can making Photocurable resin composition is solidified remains suitable value.Thus, the numerical value of these SP values and glass transition temperature of take is cause, can improve chemical proofing and the anti-dyeability of functional panel.Further, photopolymerization monomer can play as the effect to the effective diluent of optical polymerism oligomer, and Photocurable resin composition is easy to present appropriate viscosity, also can give good coating.
In addition, in above-mentioned Photocurable resin composition, as monomer, except the photopolymerization monomer of the above-mentioned SP value with regulation, in the scope of not damaging effect of the present invention, can further contain the monomer except above-mentioned photopolymerization monomer.That is, when coordinating other monomers, as long as the SP value that SP value by other monomers is separately calculated according to above-mentioned formula (X) is in the scope of above-mentioned SP value.
In above-mentioned Photocurable resin composition, can use known Photoepolymerizationinitiater initiater.This Photoepolymerizationinitiater initiater plays the effect that causes the polymerization of above-mentioned photopolymerization monomer and optical polymerism oligomer by irradiation ultraviolet radiation.As this Photoepolymerizationinitiater initiater, particularly, for example can list the 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, 2,2-dimethoxy-2-phenyl acetophenone, acetophenone diethyl ketal, the alkoxy benzene ethyl ketone, the benzil dimethyl ketal, benzophenone and 3,3-dimethyl-4-methoxy benzophenone, 4,4-dimethoxy-benzophenone, the benzophenone derivates such as 4,4-diaminobenzophenone, the Benzoylbenzene alkyl formate, two (4-dialkyl amido phenyl) ketone, the benzil derivatives such as benzil and benzil methyl ketal, the benzoin derivatives such as benzoin and benzoin isobutyl ether, the benzoin isopropyl ether, 2-hydroxy-2-methyl propiophenone, the 1-hydroxycyclohexylphenylketone, xanthone, thioxanthones and thioxanthone derivates, fluorenes, TMDPO, two (2,6-dimethoxy benzoyls)-2,4,4-tri-methyl-amyl phosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxides, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino acetone-1, 2-benzyl-2-dimethylamino-1-(morpholino phenyl)-butanone-1 etc.These Photoepolymerizationinitiater initiaters can be used separately a kind of, also can be used in combination of two or more.It is desirable to, with respect to summation 100 mass parts of above-mentioned photopolymerization monomer and optical polymerism oligomer, the amount of the scope that the use level of the Photoepolymerizationinitiater initiater in above-mentioned Photocurable composition is 0.1～10 mass parts.
When the use level of Photoepolymerizationinitiater initiater is less than 0.1 mass parts, the effect of initiated polymerization is little, and on the other hand, while surpassing 10 mass parts, the effect of initiated polymerization can be saturated, and in addition, the cost of raw material can increase.
In addition, in above-mentioned Photocurable composition, consider required solidification reactivity, stability etc., can further contain as required sensitising agent.This sensitising agent has following effect: absorb energy by being irradiated by light, this energy or electronics move in polymerization initiator and carry out initiated polymerization.As this sensitising agent, can enumerate ESCAROL 507 isopentyl ester etc.It is desirable to, with respect to summation 100 mass parts of above-mentioned photopolymerization monomer and optical polymerism oligomer, the amount of the scope that the use level of these sensitising agents is 0.1～10 mass parts.
And then, in above-mentioned Photocurable resin composition, consider needed solidification reactivity, stability etc., can further contain as required polymerization inhibitor.As this polymerization inhibitor, can list quinhydrones, hydroquinone monomethyl ether, p methoxy phenol, 2,4-dimethyl-6-tert-butyl phenol, BHT, butylated hydroxy anisole, 3-hydroxyl thiophenol, alpha-nitroso-beta-naphthol, 1,4-benzoquinone, 2,5-dihydroxy paraquinones etc.It is desirable to, with respect to summation 100 mass parts of above-mentioned photopolymerization monomer and optical polymerism oligomer, the amount of the scope that the use level of these polymerization inhibitors is 0.1～10 mass parts.
In addition, the Photocurable resin composition used in the formation of above-mentioned coating layer can contain the organic solvents such as ether as retarder thinner, ketone, ester, as this organic solvent, can list propylene glycol monomethyl ether acetate (PMA), MEK (MEK), methyl iso-butyl ketone (MIBK) (MIBK), acetone or butyl lactate etc.These retarder thinners can be used separately a kind of, also can be used in combination of two or more.
Above-mentioned Photocurable composition is used retarder thinner as described above as required, makes it into coating aqueous, and it is coated on the face on base material.The method of coating can adopt known method, can list heliogravure rubbing method (gravure coating), print roll coating method, reversion type rubbing method (reverse coating), scraper for coating method (knife coating), mould rubbing method (die coating), lip rubbing method (lip coating), scrapes formula rubbing method (doctor coating), extrusion coated method (extrusion coating), slip rubbing method (slide coating), line rod rubbing method, curtain coating method (curtain coating), extrusion coated method, method of spin coating etc.
[coating layer]
Above-mentioned Photocurable composition is coated on base material, then made its photocuring, thereby form coating layer on substrate layer.The glass transition temperature of the coating layer formed is more than 50 ℃, is preferably more than 70 ℃, more preferably more than 80 ℃.The higher limit of glass transition temperature is not particularly limited, the viewpoint of the easiness of starting with from raw material etc., and it is desirable being generally below 200 ℃.The glass transition temperature of coating layer is in above-mentioned scope the time, and the effect that the SP value had with above-mentioned photopolymerization monomer is cause interacts, and can more improve chemical proofing and the anti-dyeability of functional panel.Particularly in anti-dyeability, bring into play significant effect.
As the method for the Photocurable composition photocuring that makes above-mentioned coating, the method for irradiation ultraviolet radiation is generally arranged.Face on the substrate layer of formation coating layer can be the one side in surface and the back side, can be also two-sided, suitably selects as required to get final product.In addition, the exposure of the light when Photocurable composition is solidified, adopting in ultraviolet situation, and usually, exposure intensity is 20～2000mW/cm 2, exposure is 100～5000mJ/cm 2.
The thickness of above-mentioned coating layer can suitably be selected according to the degree of desired aesthetic property, chemical proofing, is not particularly limited, and usually is expected to be the thickness of the scope of 1 μ m～200 μ m.
In addition, in the situation that irradiation ultraviolet radiation, because the ultraviolet curing reaction is radical reaction, therefore easily is subject to the obstruction of oxygen.Therefore, after above-mentioned Photocurable composition is coated to base material, solidify said composition in order to avoid contacting with oxygen under nitrogen atmosphere.
[substrate layer]
As the material of the substrate layer used in functional panel of the present invention, can list the inorganic material such as asbestos shingle (slate), concrete, metal, calcium silicates, calcium carbonate, glass; Wood materials, and the organic material such as polypropylene, polystyrene, Merlon, unsaturated polyester resin; And their composite.Wherein, be preferably the material that adds the fibers such as glass fibre, carbon fiber are arranged to form in organic material, i.e. so-called FRP (fiber reinforced plastic, fibre reinforced plastics).As FRP, can list the sheet molding compound (SMC) (SMC of the sheet that comprises unsaturated polyester resin, filler and glass fibre or carbon fiber, sheet molding compound), for BMC (bulk molding compound, BMC) with the same composite of SMC and the bulk that comprises short fiber etc.Generally, FRP is combined with thermosetting resin, organic peroxide (curing agent), filler, shrinking agent, internal mold release, strengthening material, crosslinking agent and tackifier etc., FRP is used as follows: put it in the mould that is set as predetermined temperature, pressurizeed, be shaped to the shape of the position that is suitable as Building Material House's configuration.Wherein, so long as comprise unsaturated polyester (UP) as thermoplastic resin, filler and as the glass fibre of strengthening material or the FRP of carbon fiber, just can further improve the intensity of gained functional panel integral body and durability etc.
As unsaturated polyester (UP), can be generated by polyalcohols such as the unsaturated acids of the polyacids such as maleic anhydride, fumaric acid and ethylene glycol, propane diols, diethylene glycol, DPG, 1,3-PD, TMPD, neopentyl glycol, trimethyl propane mono allyl ether, A Hydrogenated Bisphenol A, bis-phenol dioxy propyl ethers.
As filler, can list calcium carbonate, aluminium hydroxide etc.Viewpoint from reducing costs, be preferably calcium carbonate, and the viewpoint from the chemical proofing that improves FRP self, be preferably aluminium hydroxide.If yet be formed as described above above-mentioned coating layer, even adopt to use calcium carbonate as the FRP of filler as base material, also can fully improve the chemical proofing of functional panel integral body, therefore can easily realize thering is the functional panel by the substrate layer that FRP forms cheaply.
As glass fibre and the carbon fiber of strengthening material, can use aptly fibre length is the fiber that about 20～50mm, fibre diameter are 5～25 μ m left and right, and it is desirable in FRP, with the amount of 10～70 quality %, containing.The FRP used as above-mentioned substrate layer can manufacture as follows: mix these compositions, utilize FRP manufacturing installation etc. to form and have predetermined thickness and big or small FRP.
In addition, the thickness of substrate layer can change according to the purposes of functional panel, more than being generally 2.5mm.The upper limit of thickness is not particularly limited, and can suitably select.
[functional panel]
Functional panel of the present invention comprises above-mentioned coating layer and substrate layer, and this coating layer is formed on this substrate layer and forms.More than the thickness of functional panel integral body is preferably 2.5mm usually.The upper limit of the thickness of functional panel integral body is not particularly limited, can form above-mentioned coating layer in surface and this two sides, the back side on substrate layer, as required, can be also to be formed with the sandwich construction in the intermediate layer formed by various materials on the basis of these substrate layers and coating layer, between these layers.Now, above-mentioned coating layer is brought into play excellent chemical proofing and anti-dyeability as mentioned above, therefore it is desirable to this coating layer is formed the most surface layer of functional panel.As intermediate layer, for example can list the priming coat of the cementability for improving substrate layer and coating layer, for the aesthetic property that improves functional panel, decorative layer that given decorative pattern, color etc.
The functional panel of the present invention so obtained is formed with above-mentioned specific coating layer on substrate layer, so chemical proofing and anti-dyeability excellence, even and use the strong washing agent of excitant that comprises acid, alkali also to be not easy to occur rotten, deteriorated.In addition, even use the such coloring agent of hair dye also to be not easy to occur variable color, dyeing.Therefore, the suitable especially conduct of functional panel of the present invention is disposed at the bathroom of premises or the functional panel in kitchen.
In addition, if adopt the FRP that comprises unsaturated polyester resin and glass fibre or carbon fiber as substrate layer, can realize not only having given resistance chemistry moral character and anti-dyeability but also further give the functional panel of excellent durability.
Below, based on embodiment, the present invention is specifically described, but the present invention is not limited to these embodiment.
Embodiment
[preparation of Photocurable resin composition]
According to content shown in table 1, drop into 60 mass parts optical polymerism oligomer and 40 mass parts photopolymerization monomers in agitating device, mixed, (IRGACURE 184 then to add 1 mass parts Photoepolymerizationinitiater initiater, Ciba Specialty Chemicals Inc. manufactures), stir 2 minutes, and implement defoaming treatment, obtain Photocurable resin composition (C1～C11).
[table 1]
Figure BPA00001308007000181
[embodiment 1]
The Photocurable resin composition C1 of the above-mentioned preparation of coating on the base material upper surface formed by FRP (DIC マ Star ト (registration mark) 2415, DIC Kako Inc. manufactures), making its thickness is 20 μ m.Then, irradiate UV (1000mW/cm 2, 4000mJ/cm 2) Photocurable resin composition C 1 is solidified, obtain functional panel.
[embodiment 2～6]
Except the Photocurable resin composition C2～C6 that uses various above-mentioned preparations, according to embodiment 1, obtain functional panel.
[comparative example 1～5]
Except the Photocurable resin composition C7～C11 that uses various above-mentioned preparations, according to embodiment 1, obtain functional panel.
(1) mensuration of glass transition temperature
Use dynamic viscoelastic device (DMS6100, Seiko Instruments Inc. manufactures), measuring frequency: 1.0Hz, programming rate: the mensuration of carrying out glass transition temperature (Tg) under the condition of 3.0 ℃/min.
(2) evaluation of chemical proofing
Use the functional panel obtained in embodiment 1, under each condition the dipping following shown in chemicals, the variation of overview function panel, degree for this variation, use colour difference meter (SpectroEye, Sakata Inx Eng.Co., Ltd. manufactures) obtain dipping position and the Lab aberration (Δ E) that does not flood position based on following formula (A).
ΔE＝(Δa 2+Δb 2+ΔL 2) 1/2...(A)
This numerical value is less to be meaned the patience of chemicals better, is preferably below 3.0, more preferably below 1.0.It is substantially unconverted 1.0, can be considered when following.
In addition, example 1 in contrast, and the base material that uses the above-mentioned FRP by uncoated Photocurable resin composition to form, carry out the evaluation of chemical proofing equally.
HCl... in the HCl aqueous solution of 3 quality % concentration, flood 1 hour.
NaOH... in the NaOH aqueous solution of 5 quality % concentration, flood 1 hour.
BM... in commercially available washing agent (powerful spraying (power spray)/Magiclean Bathroom Cleaner (registration mark), Kao Corp manufactures), flood 24 hours.
These the results are shown in table 2.
[table 2]
HCl NaOH Commercially available washing agent
Reference examples 1 6.34 0.13 7.78
Embodiment 1 1.09 0.60 0.83
(3) anti-chromatic evaluation
Coating above-mentioned Photocurable resin composition (C1～C11) on glass substrate, making its thickness is 1.0mm.Under blanket of nitrogen, irradiate UV (1000mW/cm 2, 4000mJ/cm 2) Photocurable resin composition (C1～C11) is solidified, obtain each sample.
Use the gained sample, at commercially available hair dye (GATSBY Turn Color Natural Black (registration mark): the mixture of agent 1 and agent 2, Mandom Corp. manufactures) 24 hours after washings of middle dipping, same with the evaluation of above-mentioned (1) chemical proofing, use above-mentioned colour difference meter and obtain dipping position and the Lab aberration (Δ E) that does not flood position based on formula (A).These the results are shown in table 1.
Known according to the above results, functional panel of the present invention, when keeping good chemical proofing, is brought into play the effect of anti-dyeability excellence.Particularly in the situation that adopt the low pole materials such as (methyl) acrylate isobornyl thiocyanoacetate or dihydroxymethyl tristane two (methyl) acrylate as photopolymerization monomer, with the situation that adopts high polar substances, compare, anti-dyeability significantly reduces.

Claims (2)

1. a functional panel, is characterized in that, it comprises: making by solubility parameters SP value is 17.0(J/cm 3) 0.5above and 20.0(J/cm 3) 0.5the Photocurable resin composition that following photopolymerization monomer and optical polymerism oligomer obtain solidifies and forms and glass transition temperature is the coating layer more than 50 ℃, and substrate layer;
Described photopolymerization monomer is the monomer shown in following formula (1),
（CH 2=CR 1COO） nR 2……（1）
In formula (1), R 1mean hydrogen atom or methyl, R 2mean the n valency alkyl of carbon number 5～20, n means 1～4 integer;
The use level of described photopolymerization monomer and described optical polymerism oligomer is, is the amount of 70:30～30:70 by quality ratio;
Described substrate layer is formed by the material that comprises unsaturated polyester resin, filler and glass fibre or carbon fiber.
2. functional panel according to claim 1, it is characterized in that, described photopolymerization monomer is freely (methyl) isobornyl acrylate of choosing, 1, 6-hexylene glycol two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, (methyl) acrylic acid isopentyl ester, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, the different myristin of (methyl) acrylic acid, (methyl) stearyl acrylate alcohol ester, the 3-methyl isophthalic acid, 5-pentanediol two (methyl) acrylate, two (methyl) acrylic acid DOPCP, cyclohexanedimethanol two (methyl) acrylate, two (methyl) acrylic acid-1, 9-nonanediol ester, trimethylolpropane tris (methyl) acrylate, at least one monomer in the group that pentaerythrite four (methyl) acrylate forms.
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JP2012224669A (en) * 2011-04-15 2012-11-15 Mitsubishi Rayon Co Ltd Active energy ray-curable coating material composition, and coated article
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001240774A (en) * 2000-02-29 2001-09-04 Hitachi Chem Co Ltd Method of producing layer having both hydrophilic antifoulancy and hard coat and plastic molded product to be obtained by this method
CN1406259A (en) * 2000-12-28 2003-03-26 纳托科株式会社 Urethane (meth) acrylate curable with actinic radiation, compositions curable therewith, and use of both
CN101013291A (en) * 2006-02-02 2007-08-08 株式会社普利司通 Conductive elastic roller and image forming apparatus comprising the same
CN101052681A (en) * 2004-11-08 2007-10-10 三菱化学株式会社 Radiation curable composition and curing product thereof, and laminate including the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3963239B2 (en) * 1998-04-07 2007-08-22 日本化薬株式会社 Resin composition, lens resin composition and cured product thereof
US6713551B2 (en) * 2000-07-19 2004-03-30 Nippon Shokubai Co., Ltd. Resin composition for coating and coating composition for curing
US20080102262A1 (en) * 2004-11-08 2008-05-01 Mitsubishi Chemical Corporation Radiation Curable Composition and Curing Product Thereof, and Laminate Including the Same
JP2007131698A (en) * 2005-10-11 2007-05-31 Mitsubishi Chemicals Corp Radiation-curable composition, cured material of the same and laminated material of the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001240774A (en) * 2000-02-29 2001-09-04 Hitachi Chem Co Ltd Method of producing layer having both hydrophilic antifoulancy and hard coat and plastic molded product to be obtained by this method
CN1406259A (en) * 2000-12-28 2003-03-26 纳托科株式会社 Urethane (meth) acrylate curable with actinic radiation, compositions curable therewith, and use of both
CN101052681A (en) * 2004-11-08 2007-10-10 三菱化学株式会社 Radiation curable composition and curing product thereof, and laminate including the same
CN101013291A (en) * 2006-02-02 2007-08-08 株式会社普利司通 Conductive elastic roller and image forming apparatus comprising the same

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