CN102112306A - Functional panel - Google Patents

Functional panel Download PDF

Info

Publication number
CN102112306A
CN102112306A CN2009801299643A CN200980129964A CN102112306A CN 102112306 A CN102112306 A CN 102112306A CN 2009801299643 A CN2009801299643 A CN 2009801299643A CN 200980129964 A CN200980129964 A CN 200980129964A CN 102112306 A CN102112306 A CN 102112306A
Authority
CN
China
Prior art keywords
methyl
acrylate
functional panel
monomer
acrylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2009801299643A
Other languages
Chinese (zh)
Other versions
CN102112306B (en
Inventor
石原健延
赤间秀洋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bridgestone Corp
Original Assignee
Bridgestone Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bridgestone Corp filed Critical Bridgestone Corp
Publication of CN102112306A publication Critical patent/CN102112306A/en
Application granted granted Critical
Publication of CN102112306B publication Critical patent/CN102112306B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B32B27/06—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
    • 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

Landscapes

  • 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)
  • Finishing Walls (AREA)
  • Paints Or Removers (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 by use specific photopolymerization monomer improves chemical proofing and anti-chromatic functional panel.
Background technology
As the functional panel of structure material is the wall of wall, floor or ceiling as building and the member that disposes is given various functions such as soundproof effect, humidity regulation according to the position of its configuration.Especially when the member of using as the water places such as bathroom, toilet or kitchen of premises uses, require to have 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 on the bottom coating on the surface that is formed at base material, further be formed with the decorative panel of filming in the top layer that formed by ultra-violet solidified acrylate coating.When using this decorative panel, demonstrate excellent hot water resistance, hardness property, solid sense, soil resistance etc., and be difficult to produce and expand, peel off etc. as the member in aforesaid water place.
On the other hand, in recent years, in the wall of premises, particularly bathroom, toilet or the kitchen, the chance that use is combined with coloring agents such as the washing agent, hair dye of the strong and stimulating of acid etc. increases, because of these chemical reagent adhere to, not only can produce rotten, the deterioration of wall, also can cause variable color, dyeing.Unquestionable rotten, deterioration is not wish the phenomenon that takes place, and, variable color just recovers less than color originally in case taking place, if dye, also be difficult to return to color originally as time passes all the more in addition, this also is a reason of not wishing to take place 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, deterioration, 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, as patent documentation 1 is disclosed, when employing is formed with functional panel that the top layer films as the panel under the harsher environment for use, for all is rotten, deterioration, variable color and the dyeing of cause with these washing agent, coloring agent etc., might not bring into play sufficient tolerance, room for improvement is still arranged.
Therefore, the generation of rotten, the deterioration that the object of the present invention is to provide that coloring agents such as a kind of washing agent that not only can tolerate the strong and stimulating that is increased by frequency of utilization in recent years, hair dye cause also can tolerate the functional panel of the generation of variable color, dyeing.
The scheme that is used to deal with problems
The inventor is in order to address the above problem discovery, use the Photocurable resin composition that has the photopolymerization monomer of specific solubility parameters (SP value) and show specific glass transition temperature by adopting, can access the also excellent functional panel of chemical proofing and anti-dyeability, thereby finish 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 a coating layer more than 50 ℃; And substrate layer.
In addition, it is desirable to, the aforementioned lights polymerizable monomer is the monomer shown in the following formula (1),
(CH 2＝CR 1COO) nR 2......(1)
(in the formula (1), R 1Expression hydrogen atom or methyl, R 2The n valency alkyl of expression carbon number 5～20.N represents 1～4 integer.)
Further, the aforementioned lights polymerizable monomer is preferably and is selected from by (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, (methyl) acrylic acid-1,9-nonanediol ester, trimethylolpropane tris (methyl) acrylate, at least a monomer in the group that pentaerythrite four (methyl) acrylate is formed.
In addition, it is desirable to, the use level of aforementioned lights polymerizable monomer and aforementioned lights polyreactive oligomers is, is 70: 30～30: 70 amount 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 the coloring agents such as washing agent, hair dye that contain acid, can not only fully suppress to go bad, deterioration, can also fully suppress variable color, dyeing.Therefore, functional panel of the present invention is fit to be used as the member that the water places such as bathroom, toilet or kitchen of premises are used very much.In addition, be not to form other layer such as priming coat, as long as the coating layer that is formed by specific Photocurable resin composition is set, just can easily realize the functional panel of sufficient chemical proofing and anti-dyeability excellence on base material.
When particularly the material that comprises unsaturated polyester resin, filler and glass fibre or carbon fiber in employing is as base material, can access the functional panel that on the basis of these characteristics, further keeps good durability.
The specific embodiment
Below, be elaborated at the present invention.
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 a coating layer more than 50 ℃; And substrate layer.
[photopolymerization monomer]
Photopolymerization monomer used in the 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 the 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 is meant the value of calculating according to the Fedors method, and the low more expression photopolymerization monomer polarity of this value is weak more.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) 0.5More than.
If show the photopolymerization monomer of such SP value, then can keep the good compatibility with aftermentioned optical polymerism oligomer, effectively reduce the polarity that this monomer self is had simultaneously.And, because employed photopolymerization monomer is low pole, therefore can infer, solidify when forming coating layer the reactivity of the coating layer self after can fully suppressing to solidify at the optical polymerism resin combination that will obtain thus.Like this, the of the present invention functional panel that is formed with above-mentioned coating layer can not produce unnecessary reaction with cleaning agent, coloring agent etc., and can show good chemical proofing and anti-dyeability.Particularly in anti-dyeability, bring into play significant effect.
Above-mentioned photopolymerization monomer preferably uses has an above acryloxy (CH 2=CHCOO-) or methacryloxy (CH 2=C (CH 3) COO-) and (methyl) acrylate monomer, can be in simple function monomer, difunctionality monomer and the multi-functional monomer any one.
As the simple function monomer, for example can list 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) acrylic acid-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 butoxy ethyl ester, (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) isocyanuric acid ester 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, for example can list 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 alone, and also can be used in combination of two or more.
SP value when in addition, using two or more photopolymerization monomer is meant that SP that the various monomer of SP value that this monomer is had had is on duty with each cooperation ratio (is the ratio of each monomer of 1 o'clock with the monomer total amount) and value that these adductions are got.For example, with respect to photopolymerization monomer total amount 1, with the SP value be that 19.0 photopolymerization monomer is 3/4, the SP value is that 21.0 photopolymerization monomer is 1/4 a amount when cooperating, and obtains the SP value of employed 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 the following formula (1).
(CH 2＝CR 1COO) nR 2......(1)
In the above-mentioned formula (1), R 1Expression hydrogen atom or methyl.
In the above-mentioned formula (1), R 2The n valency alkyl of expression carbon number 5～20 does not contain hetero atom, can be ring-type for chain yet.In addition, in the group-CH 2-can use-the CH=CH-replacement.N represents 1～4 integer.
That is, in above-mentioned formula (1), for example be chain and be under the situation of saturated monomer, R during n=1 2Be the alkyl of carbon number 5～20, R during n=2 2Alkylidene for carbon number 5～20.And then, for chain and when being saturated monomer, R during n=3 2For three of carbon number 5～20 replaces alkyl group (alkane triyl), be that four of carbon number 5～20 replace alkyl group (alkane tetrayl) during n=4.As such R 2, for example have-CH 2CH 3,-CH 2CH 2CH 3,-CH (CH 3) CH 3, 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 shown in following formula (2), four replacement alkyl groups shown in following formula (3) etc.
[Chemical formula 1]
[Chemical formula 2]
Figure BPA00001308007000072
R 2Carbon number less than 5 o'clock, under the situation of alkyl that is chain, the SP value of monomer has the tendency of rising, under the situation of alkyl that is ring-type, obtain itself become the difficulty.In addition, R 2Carbon number surpass at 20 o'clock, under the situation of alkyl that be chain, the glass transition temperature of gained Photocurable resin composition has to reduce and is inclined to, under the situation of alkyl that is 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, coloring agents such as hair dye are easy to be penetrated into coating layer inside, so panel might be colored.
As the monomer shown in the 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 has cyclic hydrocarbon group, more preferably (methyl) isobornyl acrylate, dihydroxymethyl tristane two (methyl) acrylate.If be such monomer, then have SP value preferably, therefore have the tendency that shows good low pole, can further improve the chemical proofing and the anti-dyeability of the functional panel of gained.In addition, also can bring into play function effectively 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 is meant, 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 that has in a part.Functional group's number is 1 o'clock, and crosslink density has the tendency of rising, but owing to improves glass transition temperature thereby can access the functional panel that is formed with good chemical proofing of performance and anti-chromatic coating layer.Be preferably the photopolymerization monomer with ring-shaped structure this moment aspect the raising glass transition temperature.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 suppress effectively coloring agent, to be penetrated into coating layer inner and make the phenomenon of panel dyeing.Therefore in this case, the functional panel of the coating layer with suitable curing can kept obtaining to be formed with under chemical proofing and the state of anti-the dyeability effectively.
[optical polymerism oligomer]
As the optical polymerism oligomer that uses in the above-mentioned Photocurable resin composition, particularly, for example can list 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 followingly synthesize: by the reactions such as 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; Perhaps make polyisocyanate compound and (methyl) acrylate compounds carry out urethane with hydroxyl.
Above-mentioned optical polymerism oligomer can be any one in simple function oligomer, Difunctional oligomers, the multifunctional oligomer, and the viewpoint from the crosslink density of the appropriateness that realizes the gained Photocurable resin composition is preferably multifunctional oligomer.
In these optical polymerism oligomer,, be preferably polyurethane series (methyl) acrylate oligomer from giving viewpoint as the suitable characteristic except that chemical proofing and anti-dyeability of functional panel.Polyurethane series (methyl) acrylate oligomer, (methyl) acrylate that for example can come the synthesis of polyurethane prepolymer by polyalcohol and polyisocyanates, this polyurethane prepolymer addition is had a hydroxyl is made, and it can be polyurethane series (methyl) acrylate oligomer with carbonic ester skeleton.
The synthetic middle polyalcohol that uses of above-mentioned polyurethane prepolymer is for having the compound of a plurality of hydroxyls (OH yl), particularly, can list PPG, PEPA, gather 1,4-butanediol, polybutadiene polyol, alkylene oxide modified polybutadiene polyalcohol and polyisoprene polyalcohol etc.These polyalcohols can be used alone, and also can be used in combination of two or more.In addition, above-mentioned PPG can get by addition polymerization, for example makes polyalcohol additions such as 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, what for example can list that ring-opening polymerisation by oxolane (THF) gets is poly-1, the 4-butanediol.
Above-mentioned PEPA also can get by addition polymerization, for example can be by ethylene glycol, diethylene glycol, 1,4-butanediol, 1, polyalcohols such as 6-hexylene glycol, propane diols, trimethylolethane, trimethylolpropane are with polybasic carboxylic acids such as adipic acid, glutaric acid, butanedioic acid, decanedioic acid, pimelic acid, suberic acids and get.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 gets is PEPA.
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, carbodiimides modifier, glycol modification thing etc.These polyisocyanates can be used alone, and 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 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; Inorganic tin compounds such as stannous chloride; Organo-lead compounds such as octene lead plumbate; Cyclic amines such as triethylenediamine; Organic sulfonic acids such as p-methyl benzenesulfonic acid, pyrovinic acid, fluosulfonic acid; Inorganic acids such as sulfuric acid, phosphoric acid, perchloric acid; Bases such as sodium alkoxide, lithium hydroxide, aluminium alcoholates (aluminum alcoholate), NaOH; 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 alone, and also can be used in combination of two or more.With respect to the above-mentioned polyalcohol of 100 mass parts, above-mentioned catalyst consumption is preferably the amount of the scope of 0.001～2.0 mass parts.
In addition, above-mentioned and (methyl) the polyurethane prepolymer addition, 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.Have the acrylate of hydroxyl as this, can list acrylic acid-2-hydroxyl ethyl ester, acrylic acid-2-hydroxypropyl acrylate, pentaerythritol triacrylate etc.These acrylate with hydroxyl can be used alone, and also can be used in combination of two or more.
By such optical polymerism oligomer is cooperated with above-mentioned photopolymerization monomer, as described later, the glass transition temperature that the coating layer that can optimization gained Photocurable resin composition solidifies 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 that uses in the 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 be generally 70: 30～30: 70, be preferably 40: 60～60: 40 amount.When the use level of monomer was very few, the viscosity of possible gained Photocurable resin composition rose, the coating variation, and might can't give full play to rerum naturas such as chemical proofing and anti-dyeability.In addition, when the use level of monomer is too much, has 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, then can give full play to the low pole that photopolymerization monomer has, and can make glass transition temperature remain suitable value the coating layer after the Photocurable resin composition curing.Thus, be cause with the numerical value of these SP values and glass transition temperature, can improve the 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 the viscosity of appropriateness, also can give good coating.
In addition, in above-mentioned Photocurable resin composition,, except that the photopolymerization monomer of above-mentioned SP value with regulation, in the scope of not damaging effect of the present invention, can further contain the monomer except that above-mentioned photopolymerization monomer as monomer.That is, when cooperating other monomers, as long as the SP value of being calculated by other monomers SP value above-mentioned formula of foundation (X) separately 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; the 4-dimethoxy-benzophenone; 4; benzophenone derivates such as 4-diaminobenzophenone; the Benzoylbenzene alkyl formate; two (4-dialkyl amido phenyl) ketone; benzil derivatives such as benzil and benzil methyl ketal; benzoin derivatives such as benzoin and benzoin isobutyl ether; the benzoin isopropyl ether; 2-hydroxy-2-methyl propiophenone; the 1-hydroxycyclohexylphenylketone; xanthene ketone; thioxanthones and thioxanthone derivates; fluorenes; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; two (2; 6-dimethoxy benzoyl)-2; 4; 4-tri-methyl-amyl phosphine oxide; two (2; 4, the 6-trimethylbenzoyl)-phenyl phosphine oxide; 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 alone, and 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 use level of the Photoepolymerizationinitiater initiater in the above-mentioned Photocurable composition is the amount of the scope of 0.1～10 mass parts.
The use level of Photoepolymerizationinitiater initiater is during less than 0.1 mass parts, and the effect of initiated polymerization is little, and on the other hand, when 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 sensitising agent as required.This sensitising agent has following effect: absorb energy by being penetrated by illumination, this energy or electronics move to and come initiated polymerization in the polymerization initiator.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 use level of these sensitising agents is the amount of the scope of 0.1～10 mass parts.
And then, in above-mentioned Photocurable resin composition, consider needed solidification reactivity, stability etc., can further contain polymerization inhibitor as required.As this polymerization inhibitor, can list quinhydrones, hydroquinone monomethyl ether, p methoxy phenol, 2,4-dimethyl-6-tert-butyl phenol, 2,6-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 use level of these polymerization inhibitors is the amount of the scope of 0.1～10 mass parts.
In addition, the Photocurable resin composition that uses in the formation of above-mentioned coating layer can contain 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 alone, and also can be used in combination of two or more.
Above-mentioned Photocurable composition uses retarder thinner as described above as required, and it is aqueous to make it into coating, and it is coated on the face on the base material.The method of coating can adopt known method, can list heliogravure rubbing method (gravure coating), the print roll coating method, reversion type rubbing method (reverse coating), scraper rubbing method (knife coating), mould rubbing method (die coating), lip rubbing method (lip coating), scrape formula rubbing method (doctor coating), extrusion coated method (extrusion coating), slip rubbing method (slide coating), line rod rubbing method, curtain formula rubbing method (curtain coating), extrusion coated method, method of spin coating etc.
[coating layer]
Above-mentioned Photocurable composition is coated on the base material, then made its photocuring, thereby on substrate layer, form coating layer.The glass transition temperature of the coating layer that forms 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 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 SP value that is had with above-mentioned photopolymerization monomer can more improve the chemical proofing and the anti-dyeability of functional panel for the effect of cause interacts.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 arranged generally.Face on the substrate layer of formation coating layer can be the one side in the surface and the back side, also can be two-sided, suitably selects as required to get final product.In addition, the exposure of the light when Photocurable composition is solidified is adopting under the 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 is expected to be the thickness of the scope of 1 μ m～200 μ m usually.
In addition, under the situation of irradiation ultraviolet radiation,, therefore be subjected to the obstruction of oxygen easily because the ultraviolet curing reaction is radical reaction.Therefore, after above-mentioned Photocurable composition is coated base material, in order to avoid contacting with oxygen and under nitrogen atmosphere, solidify said composition.
[substrate layer]
As the material of the substrate layer that uses in the functional panel of the present invention, can list inorganic material such as asbestos shingle (slate), concrete, metal, calcium silicates, calcium carbonate, glass; Wood materials, and organic material such as polypropylene, polystyrene, Merlon, unsaturated polyester resin; And their composite.Wherein, be preferably the material that adding has fibers such as glass fibre, carbon fiber to form in organic material, promptly 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 with the same composite of SMC and comprise BMC (bulk molding compound, BMC) of the bulk of 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., the following use of FRP: put it in the mould that is set at predetermined temperature, pressurize, 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, just can further improve functional panel integral intensity of gained and durability etc. as the glass fibre of strengthening material or the FRP of carbon fiber.
As unsaturated polyester (UP), can be by the unsaturated acids of polyacids such as maleic anhydride, fumaric acid and ethylene glycol, propane diols, diethylene glycol, DPG, 1, polyalcohols such as ammediol, TMPD, neopentyl glycol, trimethyl propane mono allyl ether, A Hydrogenated Bisphenol A, bis-phenol dioxy propyl ether generate.
As filler, can list calcium carbonate, aluminium hydroxide etc.Viewpoint from reducing cost is preferably calcium carbonate, and the viewpoint from the chemical proofing that improves FRP self is preferably aluminium hydroxide.If yet be formed as described above above-mentioned coating layer, even then adopt to use calcium carbonate as the FRP of filler as base material, therefore also can fully improve the chemical proofing of functional panel integral body, can easily realize having the functional panel of the substrate layer that forms by FRP cheaply.
As the glass fibre and the carbon fiber of strengthening material, can use aptly that fibre length is about 20～50mm, fibre diameter is the fiber about 5～25 μ m, it is desirable containing with the amount of 10～70 quality % in FRP.The FRP that uses as above-mentioned substrate layer can followingly make: mix these compositions, utilize the FRP manufacturing installation to wait and form the FRP with preset thickness and size.
In addition, the thickness of substrate layer can change according to the purposes of functional panel, is generally more than the 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.The thickness of functional panel integral body is preferably more than the 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, also can be the sandwich construction that on the basis of these substrate layers and coating layer, between these layers, is formed with the intermediate layer that forms by various materials.At this moment, 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 superficial layer of functional panel.As the intermediate layer, for example can list the priming coat of the cementability that is used to improve substrate layer and coating layer, be used to improve decorative layer aesthetic property, that given decorative pattern, color of functional panel etc.
So the of the present invention functional panel that obtains 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 take place rotten, deterioration.In addition, even use the such coloring agent of hair dye also to be not easy to take place variable color, dyeing.Therefore, functional panel of the present invention is suitable to especially being 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, then can realize not only giving resistance chemistry moral character and anti-dyeability but also further give the functional panel of excellent durability as substrate layer.
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 the table 1, in agitating device, drop into 60 mass parts optical polymerism oligomer and 40 mass parts photopolymerization monomers, mix, (IRGACURE 184 then to add 1 mass parts Photoepolymerizationinitiater initiater, Ciba Specialty Chemicals Inc. makes), stirred 2 minutes, and implement defoaming treatment, and the acquisition Photocurable resin composition (C1～C11).
[table 1]
[embodiment 1]
The Photocurable resin composition C1 of the above-mentioned preparation of coating on the base material upper surface that is formed by FRP (DIC マ Star ト (registration mark) 2415, DIC Kako Inc. makes), making its thickness is 20 μ m.Then, irradiation UV (1000mW/cm 2, 4000mJ/cm 2) Photocurable resin composition C 1 is solidified, obtain functional panel.
[embodiment 2～6]
Except that the Photocurable resin composition C2～C6 that uses various above-mentioned preparations, obtain functional panel according to embodiment 1.
[comparative example 1～5]
Except that the Photocurable resin composition C7～C11 that uses various above-mentioned preparations, obtain functional panel according to embodiment 1.
(1) mensuration of glass transition temperature
Use dynamic viscoelastic device (DMS6100, Seiko Instruments Inc. makes), 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 that obtains among the 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. makes) obtain dipping position and the Lab aberration (Δ E) that does not flood the position based on following formula (A).
ΔE＝(Δa 2+Δb 2+ΔL 2) 1/2...(A)
This numerical value is more for a short time to be meaned the patience of chemicals well more, is preferably below 3.0, more preferably below 1.0.It is unconverted substantially can be considered when following 1.0.
In addition, example 1 in contrast, and the base material that uses the above-mentioned FRP by uncoated Photocurable resin composition to form carries out the evaluation of chemical proofing equally.
HCl... in the HCl aqueous solution of 3 quality % concentration, flooded 1 hour.
NaOH... in the NaOH aqueous solution of 5 quality % concentration, flooded 1 hour.
BM... in commercially available washing agent (powerful spraying (power spray)/Magiclean Bathroom Cleaner (registration mark), Kao Corp makes), flooded 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
(C1～C11), make its thickness is 1.0mm to the above-mentioned Photocurable resin composition of coating on glass substrate.Under the blanket of nitrogen, irradiation UV (1000mW/cm 2, 4000mJ/cm 2) (C1～C11) solidify obtains each sample to make Photocurable resin composition.
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. makes) 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 the position based on formula (A).These the results are shown in table 1.
According to The above results as can be known, functional panel of the present invention is brought into play the effect of anti-dyeability excellence in the good chemical proofing of maintenance.Particularly adopting under the situations of low pole material as photopolymerization monomer such as (methyl) acrylate isobornyl thiocyanoacetate or dihydroxymethyl tristane two (methyl) acrylate, comparing with the situation that adopts high polar substances, anti-dyeability significantly reduces.

Claims (5)

1. functional panel, it 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 a coating layer more than 50 ℃; And substrate layer.
2. functional panel according to claim 1 is characterized in that, described photopolymerization monomer is the monomer shown in the following formula (1),
(CH 2＝CR 1COO) nR 2......(1)
In the formula (1), R 1Expression hydrogen atom or methyl, R 2The n valency alkyl of expression carbon number 5～20, n represents 1～4 integer.
3. functional panel according to claim 1 and 2, it is characterized in that, described photopolymerization monomer is to be selected from by (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 alcohol 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 a monomer in the group that pentaerythrite four (methyl) acrylate is formed.
4. according to each described functional panel in the claim 1～3, it is characterized in that the use level of described photopolymerization monomer and described optical polymerism oligomer is, is 70: 30～30: 70 amount by quality ratio.
5. according to each described functional panel in the claim 1～4, it is characterized in that described substrate layer is formed by the material that comprises unsaturated polyester resin, filler and glass fibre or carbon fiber.
CN2009801299643A 2008-07-28 2009-07-22 Functional panel Expired - Fee Related CN102112306B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2008193412A JP5548347B2 (en) 2008-07-28 2008-07-28 Functional panel
JP2008-193412 2008-07-28
PCT/JP2009/063127 WO2010013627A1 (en) 2008-07-28 2009-07-22 Functional panel

Publications (2)

Publication Number Publication Date
CN102112306A true CN102112306A (en) 2011-06-29
CN102112306B CN102112306B (en) 2013-12-18

Family

ID=41610326

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009801299643A Expired - Fee Related CN102112306B (en) 2008-07-28 2009-07-22 Functional panel

Country Status (5)

Country Link
JP (1) JP5548347B2 (en)
KR (1) KR101196625B1 (en)
CN (1) CN102112306B (en)
TW (1) TWI417191B (en)
WO (1) WO2010013627A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5543808B2 (en) * 2010-01-25 2014-07-09 株式会社ブリヂストン Photopolymerizable composition and functional panel using the same
CN102504496A (en) * 2010-06-30 2012-06-20 上海晓宝增强塑料有限公司 Preparation method of fiber-reinforced plastic
JP2012224669A (en) * 2011-04-15 2012-11-15 Mitsubishi Rayon Co Ltd Active energy ray-curable coating material composition, and coated article
JP5860622B2 (en) * 2011-07-19 2016-02-16 株式会社ブリヂストン PHOTOCURABLE RESIN COMPOSITION, WATERWIRE MEMBER AND FUNCTIONAL PANEL USING THE SAME
JP6134473B2 (en) * 2011-07-19 2017-05-24 株式会社ブリヂストン PHOTOCURABLE RESIN COMPOSITION, WATERWIRE MEMBER AND FUNCTIONAL PANEL USING THE SAME
CN105143297B (en) 2013-04-26 2018-11-20 大赛璐湛新株式会社 Carbamate (methyl) acrylate and active energy ray-curable resin composition
KR102571283B1 (en) * 2022-01-13 2023-08-29 이영준 Tile for swimming pool and manufacturing method therefor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11292942A (en) * 1998-04-07 1999-10-26 Nippon Kayaku Co Ltd Resin composition, resin composition for lens and its cured product
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60128038T2 (en) * 2000-07-19 2007-08-09 Nippon Shokubai Co. Ltd. Curable resin and coating composition
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 (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11292942A (en) * 1998-04-07 1999-10-26 Nippon Kayaku Co Ltd Resin composition, resin composition for lens and its cured product
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

Also Published As

Publication number Publication date
KR101196625B1 (en) 2012-11-02
CN102112306B (en) 2013-12-18
WO2010013627A1 (en) 2010-02-04
TW201026497A (en) 2010-07-16
TWI417191B (en) 2013-12-01
JP2010030100A (en) 2010-02-12
KR20110038076A (en) 2011-04-13
JP5548347B2 (en) 2014-07-16

Similar Documents

Publication Publication Date Title
CN102112306B (en) Functional panel
CN103687882B (en) Light-curing resin composition, and plumbing member and functional panel using same
EP1851260B1 (en) Blush-resistant marine gel coat composition
CN101861341B (en) Low voc thermosetting composition of polyester acrylic resin for gel coat
JP6134473B2 (en) PHOTOCURABLE RESIN COMPOSITION, WATERWIRE MEMBER AND FUNCTIONAL PANEL USING THE SAME
CN103717632B (en) Photocurable resin composition and use its wet district component and functional panel
JP5735816B2 (en) Photopolymerizable composition, water-surrounding member and functional panel using the same
CN107207901A (en) Coating urethane resin compositions and the feel coating using said composition
JP2013023548A (en) Photocurable resin composition, wet area member and functional panel using the same
MXPA05001740A (en) Urethane acrylate gel coat resin and method of making.
CN102190915B (en) Light polymerization composition and functional panel having the same
JP5567325B2 (en) Photocurable resin composition and functional panel using the same
JP2018080265A (en) Active energy ray-curing resin composition
WO2012108193A1 (en) Photocurable resin composition and functional panel obtained using same
TWI425060B (en) A photopolymerizable composition and a functional panel using the same
CN106795245A (en) The method of the dirt accumulation on curable film-forming compositions and reduction base material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20131218

Termination date: 20200722