TWI417191B - Functional panel - Google Patents

Description

Functional panel

The present invention relates to a functional panel which is improved in chemical resistance and dyeing resistance by using a photocurable resin composition containing a specific photopolymerizable monomer.

The functional panel used as a building material is used as a building material provided on the wall surface of a building, a floor surface, or a wall surface of a ceiling, and is provided with various functions such as sound insulation effect and humidity adjustment property in accordance with the installation place. When such a functional panel is used in a building material for a water environment such as a bathroom, a washstand, or a kitchen in a house, it is required to have various properties such as water resistance and moisture resistance in a more severe use environment. .

A decorative film of an upper coating film formed of an ultraviolet curable acrylate resin coating material is further formed on a lower coating film formed on a surface of a substrate, as disclosed in Japanese Laid-Open Patent Publication No. Hei 11-20112. board. In the above-mentioned document, when the decorative sheet is used as a building material for a water environment as described above, it has a good temperature resistance, hardness property, thick feeling, stain resistance, and the like, and is not likely to be swollen or peeled off.

On the other hand, in recent years, there has been an increase in the use of stains such as detergents or hair dyes containing strong irritants such as acid in the wall of a house, especially in a bathroom, a washstand or a kitchen, and it is not only a wall surface due to the adhesion of these agents. Deterioration or deterioration can also cause discoloration or staining. There is no need to say that deterioration or deterioration is an undesired phenomenon, and once it is discolored, it cannot return to its original color. In addition, when dyeing occurs, it is more difficult to return to the original color as time increases, and it is undesirable to discolor or stain. The reason for the occurrence. A functional panel disposed at such a location is required to be a panel that is resistant to the use of detergents or stains without deterioration or deterioration, discoloration or staining.

However, as disclosed in the patent literature, the functional panel formed with the upper coating film serves as a panel for all deterioration, deterioration, discoloration and dyeing of these cleaning agents or dyes when used in a more severe use environment. There is not necessarily sufficient tolerance, and there is still room for improvement.

Accordingly, it is an object of the present invention to provide a function which is resistant to deterioration or deterioration of dyeing agents such as strong irritating detergents or hair dyes which are frequently used in recent years, and which is resistant to discoloration or staining. panel.

In order to solve the above problems, the inventors of the present invention have found that a photocurable resin having a specific dissolution parameter (SP value) and a photocurable resin composition having a specific glass transition temperature can be obtained with good chemical resistance. The functional panel of the property and dye resistance is further completed by the present invention.

That is, the functional panel of the present invention is characterized by comprising photocurability of a photopolymerizable monomer and a photopolymerizable oligomer having a dissolution parameter (SP value) of 20.0 (J/cm ³ ) ^0.5 or less. a coating layer comprising a resin composition which is cured and has a glass transition temperature of 50 ° C or higher; and a substrate layer.

Further, the photopolymerizable monomer is preferably a monomer represented by the following formula (1).

(CH ₂ =CR ¹ COO) _n R ² ‧‧‧‧‧‧‧(1)

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an n-valent hydrocarbon group having a carbon number of 5 to 20, and n represents an integer of 1 to 4).

Further, the photopolymerizable monomer is preferably an isodecyl (meth) acrylate, 1,6-hexanediol di(meth) acrylate, or a dimethylol tricyclodecanealkyl di(a) Acrylate, isoamyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, eighteen Alkyl (meth) acrylate, 3-methyl-1,5-pentanediol di(meth) acrylate, neopentyl glycol di(meth) acrylate, cyclohexane dimethanol di(methyl) At least one selected from the group consisting of acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate monomer.

Further, the amount of the photopolymerizable monomer and the photopolymerizable oligomer is preferably a mass ratio of 70:30 to 30:70.

Further, the base material layer is preferably made of a material containing an unsaturated polyester resin, a filler, and glass fibers or carbon fibers.

The functional panel of the present invention has good chemical resistance and dyeing resistance, and even if a dye such as an acid-containing detergent or a hair dye is adhered, not only deterioration or deterioration but also discoloration or dyeing can be sufficiently suppressed. Therefore, the functional panel of the present invention is very suitable for use as a building material for water environment such as a bathroom, a washstand or a kitchen in a house. Further, it is not necessary to form another layer such as an undercoat layer, and it is easy to achieve excellent chemical resistance and dyeing resistance by providing a coating layer formed of a specific photocurable resin composition on a substrate. Functional panel.

In particular, when a material containing an unsaturated polyester resin, a filler, and glass fiber or carbon fiber is used as a substrate, a functional panel having such characteristics and more excellent durability can be obtained.

Hereinafter, the present invention will be described in detail.

The functional panel of the present invention is characterized by comprising a photocurable resin composition comprising a photopolymerizable monomer having a solubility parameter (SP value) of 20.0 (J/cm ³ ) ^0.5 or less and a photopolymerizable oligomer. a coating layer composed of a hardened glass transition temperature of 50 ° C or higher; and a substrate layer.

[Photopolymerizable monomer]

The photopolymerizable monomer used in the photocurable resin composition is characterized in that the dissolution parameter (SP value) is 20.0 (J/cm ³ ) ^0.5 or less. The SP value (δ) is generally defined by the Moire's evaporation energy (ΔEv) and the Mohr volume (V) of the liquid of the following formula.

SP value (δ) = (δEv/V) ^0.5

Furthermore, according to the Fedors method, the SP value (Solubility Parameter Values) can be estimated only from the chemical structure (refer to the fourth edition "Polymer Handbook" compiled by J. Brandrup and other editors). Further, the SP value in the present specification means a value calculated by the Fedors method, and the lower the value, the lower the polarity of the photopolymerizable monomer. The SP value of the photopolymerizable monomer is preferably 19.6 (J/cm ³ ) ^0.5 or less, more preferably 19.4 (J/cm ³ ) ^0.5 or less. The lower limit of the SP value is not particularly limited, but is usually 17.0 (J/cm ³ ) of ^0.5 or more.

When it is a photopolymerizable monomer having such an SP value, it has good compatibility with a photopolymerizable oligomer described later, and can effectively reduce the polarity of the monomer itself. In addition, since the photopolymerizable monomer to be used has a low polarity, it is presumed that when the photopolymerizable resin composition obtained therefrom is cured to form a coating layer, the reaction of the coating layer itself after hardening can be sufficiently suppressed. Sex. Thus, the functional panel of the present invention in which the above-mentioned coating layer is formed does not cause an unnecessary reaction with a detergent or a dye, and can be found to have good chemical resistance and dyeing resistance. In particular, it has a remarkable effect on dye resistance.

The photopolymerizable monomer is preferably a (meth) group having one or more propylene decyloxy groups (CH ₂ =CHCOO-) or methacryloxycarbonyl groups (CH ₂ =C(CH ₃ )COO-). The acrylate monomer may also be any of a monofunctional monomer, a bifunctional monomer, and a polyfunctional monomer.

Monofunctional monomers such as: isodecyl (meth) acrylate, decyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentyl (meth) acrylate, two An alicyclic (meth) acrylate such as cyclopentenyl (meth) acrylate or cyclohexyl (meth) acrylate; benzyl (meth) acrylate, 4-butylcyclohexyl (methyl) Acrylate, (meth) propylene decyl porphyrin, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, pentyl (A) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (methyl) Acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, mercapto (meth) acrylate Ester, mercapto (meth) acrylate, isodecyl ( Acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, tetradecane (meth) acrylate, hexadecyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofuran (meth) acrylate, butoxy ethyl (meth) acrylate , ethoxy diethylene glycol (meth) acrylate, polyoxyethyl phenyl phenyl ether acrylate, phenoxy ethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate Ester, polypropylene glycol mono (meth) acrylate, methoxy ethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxy polyethylene glycol (meth) acrylate , methoxypolypropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3, 7- Dimethyloctyl (meth) acrylate; ether skeleton (meth) acrylate, and the like.

Bifunctional monomers such as: ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,4-butanediol Di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, gin(2-hydroxyethyl)isocyanuric acid Methyl) acrylate, tricyclodecane dimethanol di(meth) acrylate, dimethylol tricyclodecane di(meth) acrylate, bisphenol A alkylene oxide addition diol Methyl acrylate, hydrogenated bisphenol A alkylene oxide addition diol di(meth) acrylate, bisphenol A diglycidyl ether addition (meth) acrylate epoxy (Meth) acrylate, etc.

Polyfunctional monomers such as: trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tris(A) Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol Hydroxypenta(meth)acrylate and the like.

One type of these photopolymerizable monomers may be used alone or two or more types may be used in combination.

In addition, the SP value when two or more photopolymerizable monomers are used means that the SP value of each monomer is multiplied by the mixing ratio of each monomer (the ratio of each monomer when the total amount of the monomers is 1) After that, add the meaning of these values to the total. For example, the total amount of the photopolymerizable monomer is 1, and the amount of the photopolymerizable monomer having an SP value of 19.0 in an amount of 3/4 and the photopolymerizable monomer having an SP value of 21.0 is 1/4. At the time of preparation, the SP value of the entire photopolymerizable monomer to be used was determined according to the following formula (X).

SP value of photopolymerizable monomer = (19.0 × 3 / 4) + (21.0 × 1/4) = 19.5‧‧‧(X)

Among the above photopolymerizable monomers, a monomer represented by the following formula (1) is preferred.

(CH ₂ =CR ¹ COO) _n R ² ‧‧‧‧‧‧‧(1)

In the above formula (1), R ¹ represents a hydrogen atom or a methyl group.

In the above formula (1), R ² represents an n-valent hydrocarbon group having 5 to 20 carbon atoms, and does not contain a hetero atom, and may be a chain or a ring. Further, -CH ₂ - may be substituted by -CH=CH-. The n system represents an integer from 1 to 4.

That is, in the above formula (1), for example, a chain-like saturated monomer, when n=1, R ² is an alkyl group having 5 to 20 carbon atoms, and when n=2, R ² is a carbon number of 5 to 20 alkyl. Further, when a chain of the unsaturated monomer, n = 3 when R ² is a 5 to 20 carbon atoms, an alkoxy group of three (alkane-triyl), n =. 4 when R ² is a 5 to 20 carbon atoms, an alkoxy group of four (alkane-tetrayl). Such R ² may be, for example, -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH(CH ₃ )CH ₃ , cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclopentane. An alkyl group such as an alkyl group; -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )CH ₂ -isoalkylene; and an alkanetriyl group represented by the following formula (2), An alkanetetrayl group represented by the formula (3) or the like.

[Chemical Formula 1]

[Chemical Formula 2]

When the carbon number of R ² is less than 5, the SP value of the monomer tends to increase when it is a chain hydrocarbon group, and it is not easily obtained when it is a cyclic hydrocarbon group. In addition, when the carbon number of R ² exceeds 20, the glass transition temperature of the photocurable resin composition obtained when it is a chain hydrocarbon group tends to decrease, and when it is a cyclic hydrocarbon group, the photohardening is obtained. The crosslink density of the resin composition tends to decrease. It is assumed that when the crosslink density is lowered too low, since the dyeing agent such as a hair dye easily penetrates into the inside of the coating layer, the panel is stained.

The monomer represented by the above formula (1) specifically includes isodecyl (meth) acrylate, 1,6-hexanediol di(meth) acrylate, dimethylol tricyclodecyl aralkyl (Meth) acrylate, isoamyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, isotetradecyl (meth) acrylate , octadecyl (meth) acrylate, 3-methyl-1,5-pentanediol di(meth) acrylate, neopentyl glycol di(meth) acrylate, cyclohexane dimethanol (Meth) acrylate, 1,9-nonanediol di(meth) acrylate, trimethylolpropane tri(meth) acrylate, pentaerythritol tetra(meth) acrylate. Among them, from the viewpoint of increasing the glass transition temperature, it is preferably a monomer having a cyclic hydrocarbon group, more preferably an isodecyl (meth) acrylate and a dimethylol tricyclodecyl dialkyl (a) Base) acrylate. In the case of such a monomer, in order to have a more suitable SP value, a good tendency to low polarity is exhibited, and the chemical resistance and dyeing resistance of the obtained functional panel can be further improved. Further, the function of the photopolymerizable oligomer described later as a reactive diluent can be effectively exhibited.

Further, the number of functional groups of the photopolymerizable monomer is usually from 1 to 6, preferably from 1 to 4. In addition, the number of the functional groups herein means a value obtained by determining the number of the above functional groups from a plurality of molecules, and averaging the number of the obtained functional groups as a function of the number of functional groups in one molecule. When the number of functional groups is 1, the crosslinking density tends to increase, but by increasing the glass transition temperature, a functional panel formed by a coating layer which exhibits excellent chemical resistance and dye resistance can be obtained. In this case, it is preferred to increase the glass transition temperature by using a photopolymerizable monomer having a cyclic structure. On the other hand, when the number of functional groups is from 2 to 6, preferably from 2 to 4, since the crosslinking reaction of the photocurable composition can be appropriately maintained, it is presumed that it is easier to effectively suppress the infiltration of the dyeing agent in particular. The inside of the coating layer causes the panel to be dyed. Therefore, in this case, it is also possible to maintain chemical resistance and dye resistance, and to obtain a functional panel formed of a coating layer having good curability.

[Photopolymerizable oligomer]

The photopolymerizable oligomer used in the photocurable resin composition is specifically, for example, an amine ester (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, or an ether system. (Meth) acrylate oligomer, ester (meth) acrylate oligomer, polycarbonate (meth) acrylate oligomer, fluorine (meth) acrylate oligomer, fluorenone A (meth) acrylate oligomer or the like. The photopolymerizable oligomer can be obtained by using polyethylene glycol, polyoxypropylene glycol, polytetrahydrofuran, bisphenol A type epoxy resin, phenol novolak type epoxy resin, polyol, and ε-caprolactone. The adduct or the like is reacted with (meth)acrylic acid, or the polyisocyanate compound and the hydroxyl group-containing (meth) acrylate compound are subjected to amine esterification to synthesize.

The photopolymerizable oligomer may be any of a monofunctional oligomer, a difunctional oligomer or a polyfunctional oligomer, from the viewpoint of realizing an appropriate crosslinking density of the obtained photocurable resin composition. In view of this, a polyfunctional oligomer is preferred.

Among these photopolymerizable oligomers, an amine ester-based (meth)acrylate oligomer is preferred from the viewpoint of imparting excellent chemical resistance and dyeing resistance as a functional panel. . An amine ester (meth) acrylate oligomer, for example, an amino ester prepolymer can be synthesized from a polyalcohol and a polyisocyanate, and the amine ester prepolymer is added to a hydroxyl group-containing (meth) acrylate. It may be produced by an amine ester-based (meth) acrylate oligomer containing a carbonate skeleton.

The polyalcohol used in the synthesis of the above amine ester prepolymer contains a plurality of compounds of a hydroxyl group (OH group). Specifically, there are: polyether polyols, polyester polyols, polytetramethylene glycols, polybutadiene polyols, alkylene oxide modified polybutadiene polyols, and polyisoprene polyols. . One type of these polyalcohols may be used alone or two or more types may be used in combination. In addition, the above polyether polyol can be obtained by addition polymerization, such as ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and the like, addition of ethylene oxide or An alkylene oxide such as propylene oxide. Further, a polyether polyol may be obtained by ring-opening polymerization, such as a polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran (THF).

The above polyester polyol can also be obtained by addition polymerization, such as: ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, propylene glycol, trimethylolethane A polyhydric alcohol such as trimethylolpropane or a polybasic carbonic acid such as adipic acid, glutaric acid, succinic acid, sebacic acid, pimelic acid or suberic acid. Further, a polyester polyol may be obtained by ring-opening polymerization, and the polyester polyol has a lactone-based polyester polyol obtained by ring-opening polymerization of ε-caprolactone.

The polyisocyanate is a compound containing a plurality of isocyanate groups (NCO groups), specifically: toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), crude diphenylmethane diisocyanate (unprocessed MDI), and Carbaryl diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hexamethylene diisocyanate (HDI), or such isomeric cyanuric acid modification, carbodiimide modification, Glycol modification and the like. One type of these polyisocyanates may be used alone or two or more types may be used in combination.

In carrying out the synthesis of the above amine ester prepolymer, it is preferred to use a catalyst for the amine esterification reaction. The catalyst for the esterification reaction is: dibutyltin dilaurate, dibutyltin diacetate, dibutyltinthiocarboxylate, dibutyltin maleate, dioctyltinthiocarboxylate, octene Organotin compounds such as tin oxide and monobutyltin oxide; inorganic tin compounds such as chlorinated first tin; organic lead compounds such as lead octenate; cyclic amines such as tri-ethylenediamine; p-toluenesulfonic acid and methanesulfonate Organic sulfonic acid such as acid or fluorosulfonic acid; inorganic acid such as sulfuric acid, phosphoric acid or perchloric acid; alkali such as sodium methoxide, lithium hydroxide, aluminum methoxide or sodium hydroxide; tetrabutyl titanate and tetraethyl titanate. A titanium compound such as tetraisopropyl titanate; an anthracene compound; a quaternary ammonium salt or the like. These catalysts are preferably organotin compounds. A single type of these catalysts may be used, or two or more types may be used in combination. The amount of the above catalyst to be used is preferably in the range of 0.001 to 2.0 parts by weight based on 100 parts by weight of the above polyol.

Further, the (meth) acrylate having a hydroxyl group added to the above-mentioned amine ester prepolymer has one or more hydroxyl groups and has one or more (meth) acryloxy groups (CH ₂ =CHCOO- or Compound of CH ₂ =C(CH ₃ )COO-). The hydroxyl group-containing (meth) acrylate may be added to the isocyanate group of the above amine ester prepolymer. The hydroxy group-containing acrylate includes 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, and the like. One type of these hydroxy group-containing acrylates may be used, or two or more types may be used in combination.

By blending such a photopolymerizable oligomer together with the photopolymerizable monomer, the glass transition temperature of the coating layer obtained by curing the obtained photocurable resin composition can be maximized as will be described later. A photocurable resin composition which exhibits a good effect on chemical resistance and dyeing resistance is obtained.

[Photocurable resin composition]

The photocurable resin composition used in the functional panel of the present invention contains the photopolymerizable oligomer and the photopolymerizable monomer. The mass ratio of the amount of the photopolymerizable oligomer to the photopolymerizable monomer is usually 70:30 to 30:70, preferably 40:60 to 60:40. When the amount of the monomer is too small, the viscosity of the photocurable resin composition obtained increases, and the coating property deteriorates, and the chemical resistance and dyeing resistance may not be sufficiently exhibited. Further, when the amount of the monomer is too large, the flexibility of the coating film is lowered to cause a high brittleness. Therefore, when the amount of the photopolymerizable oligomer and the photopolymerizable monomer is within the above range, the low polarity of the photopolymerizable monomer can be sufficiently exhibited, and the photocurable resin composition can be cured. The glass transition temperature of the layer is maintained at an appropriate value. Thereby, the chemical resistance and dyeing resistance of the functional panel due to the values of the SP value and the glass transition temperature can be improved. Further, the photopolymerizable monomer can also act as a diluent effective for the photopolymerizable oligomer, and the photocurable resin composition can easily exhibit an appropriate viscosity and provide good coatability.

In addition, the photocurable resin composition may further contain a single sheet other than the photopolymerizable monomer, in addition to the photopolymerizable monomer having the specific SP value described above, insofar as the effects of the present invention are not impaired. body. In other words, when other monomers are blended, the SP value calculated from the SP value of the other monomer according to the above formula (X) may be within the range of the SP value.

A known photopolymerization initiator can be used for the above photocurable resin composition. By irradiating the photopolymerization initiator with ultraviolet rays, the polymerization of the photopolymerizable monomer and the photopolymerizable oligomer described above can be achieved. The photopolymerization initiator is specifically, for example, 4-dimethylamino benzoic acid, 4-dimethylamino benzoate, 2,2-dimethoxy-2-phenylacetophenone, benzene Ecetophenone diethyl ketal, alkoxyacetophenone, benzil dimethyl ketal, diphenyl ketone and 3,3-dimethyl-4-methoxy Diphenyl ketone derivatives such as bisphenyl ketone, 4,4-dimethoxydiphenyl ketone, 4,4-diaminodiphenyl ketone, benzhydryl hydrocarbyl benzoate, bis ( a benzophenone derivative such as 4-dihydrocarbylaminophenyl)one, benzophenone, and benzophenone methanol, a benzoin derivative such as benzoin and benzoin isobutyl ether, benzoin isopropyl ether, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, ketone, thioxanthone and thioxanthone derivatives, anthracene, 2,4,6-trimethylbenzhydrylbiphenyl Phosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzylidene) -Phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-ylpropanylpropane-1,2-benzyl-2-dimethylamino-1-(phenyl) Phenyl )-butanone-1 and the like. One type of these photopolymerization initiators may be used alone or two or more types may be used in combination. The amount of the photopolymerization initiator in the photocurable composition is preferably in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the photopolymerizable monomer and the photopolymerizable oligomer. .

When the amount of the photopolymerization initiator is 0.1 parts by weight or less, the effect of starting the polymerization reaction is small. On the other hand, when the amount is more than 10 parts by weight, the effect of starting the polymerization reaction is saturated and the raw material cost is increased.

Moreover, a photo-sensitive agent may be further contained as needed in consideration of curing reactivity, stability, and the like required for the photocurable composition. The light sensitive agent absorbs energy by irradiating light, and moves the energy or electrons to the polymerization starter to start polymerization. The photosensitizer may, for example, be p-dimethylamino benzoic acid isoamyl ester or the like. The amount of the photo-sensitive agent to be added is preferably in an amount ranging from 0.1 to 10 parts by weight based on 100 parts by weight of the total of the photopolymerizable monomer and the photopolymerizable oligomer.

In addition, a polymerization inhibitor may be contained as needed in consideration of curing reactivity, stability, and the like required for the photocurable resin composition. The polymerization inhibitors are: hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-third Butyl-p-cresol, butylhydroxyanisole, 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, 2,5-dihydroxy-p-quinone, and the like. The amount of the polymerization inhibitor to be added is preferably in an amount ranging from 0.1 to 10 parts by weight based on 100 parts by weight of the total of the photopolymerizable monomer and the photopolymerizable oligomer.

Further, the diluting solvent of the photocurable resin composition used for the formation of the coating layer may contain an organic solvent such as an ether, a ketone or an ester, and the organic solvent may, for example, be propylene glycol monomethyl ether acetate (PMA) or butyl. Ketone (MEK), methyl isobutyl ketone (MIBK), acetone or butyl lactate. One type of these diluent solvents may be used alone or two or more types may be used in combination.

The photocurable composition is a surface which is applied to a substrate by using a diluting solvent as needed, as described above. The coating method may be a known method, and may be exemplified by gravure coating, drum coating, reverse coating, doctor blade coating, dip coating, crack coating, and adjustment blade coating. Cloth, extrusion coating, slanting plate coating, ring bar coating, curtain coating, injection coating, rotary coating, and the like.

[coating layer]

The photocurable composition is applied onto a substrate, followed by photocuring to form a coating layer on the substrate layer. The glass transition temperature of the formed coating layer is 50 ° C or higher, preferably 70 ° C or higher, more preferably 80 ° C or higher. The upper limit of the glass transition temperature is not particularly limited, but is usually preferably 200 ° C or less from the viewpoint of availability of raw materials and the like. When the glass transition temperature of the coating layer is within the above range, it interacts with the effect of the SP value of the photopolymerizable monomer, and the chemical resistance and dyeing resistance of the functional panel can be further improved. In particular, it has a remarkable effect on dye resistance.

The method of photocuring the photocurable composition coated as described above is generally a method of irradiating ultraviolet rays. The surface on the substrate layer on which the coating layer is to be formed may be selected from one of the surface or the bottom surface, or both may be selected at the same time, and may be appropriately selected as needed. Further, the amount of light irradiation when the photocurable composition is cured by ultraviolet rays is usually 20 to 2000 mW/cm ² and the irradiation amount is 100 to 5000 mJ/cm ² .

The thickness of the coating layer which is appropriately selected depending on the degree of designability or chemical resistance required is not particularly limited, but is usually in the range of 1 μm to 200 μm.

Further, when ultraviolet rays are irradiated, since the ultraviolet curing reaction is a radical reaction, it is easily inhibited by oxygen. Therefore, after the photocurable composition is applied onto the substrate, the composition can be cured in a nitrogen atmosphere in order to avoid contact with oxygen.

[Substrate layer]

The material of the base material layer used in the functional panel of the present invention includes inorganic materials such as slate, cement, metal, calcium silicate, calcium carbonate, and glass; and wood, polypropylene, polystyrene, and polycarbonate. Organic materials such as unsaturated polyester resins; and composite materials thereof. Among them, it is preferable to add a material such as a glass fiber or a carbon fiber to an organic material, that is, a so-called FRP (Fiber Reinforced Plastics). The FRP may, for example, be an unsaturated polyester resin, a filler, and a sheet-like molding material (SMC) containing a glass fiber or a carbon fiber, and a SMC which is also a composite material and contains a short fiber. BMC (Bulk Molding Compound), etc. FRP is generally added with a thermosetting resin, an organic peroxide (hardener), a filler, a low shrinkage agent, an internal release agent, a reinforcing material, a crosslinking agent, a tackifier, etc., and is added to a specific The model of the temperature is pressurized and shaped to match the shape of the building material installation site. Among them, in the case of an unsaturated polyester containing a thermoplastic resin, a filler, and an FRP of a glass fiber or a carbon fiber which is a reinforcing material, the strength, durability, and the like of the entire functional panel obtained can be further improved.

The unsaturated polyester is an unsaturated acid of a polybasic acid such as maleic anhydride or butenedioic acid, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, trimethyl pentanediol, and neopentyl It is produced by a polyol such as a diol, a trimethylpropane monoallyl ether, a hydrogenated bisphenol, or a bisphenol diglycidyl ether.

The filler is calcium carbonate, aluminum hydroxide or the like. From the standpoint of cost reduction, calcium carbonate is preferred. From the viewpoint of improving the chemical resistance of the FRP itself, aluminum hydroxide is preferred. However, as described above, as long as the coating layer is formed, even if FRP using calcium carbonate as a filler is used as the substrate, the chemical resistance of the entire functional panel can be sufficiently improved, so that it can be easily realized at a low cost. The functional panel of the substrate layer formed by the FRP.

The glass fiber and the carbon fiber as the reinforcing material have a fiber length of about 20 to 50 mm and a fiber radius of about 5 to 25 μm, and are preferably used in an amount of 10 to 70% by mass in the FRP. The FRP used as the base material layer is mixed with these components, and an FRP having a specific thickness and size is produced by an FRP production apparatus or the like.

Further, the thickness of the substrate layer may vary depending on the use of the functional panel, but is usually 2.5 mm or more. The upper limit of the thickness is not particularly limited and may be appropriately selected.

[Functional Panel]

The functional panel of the present invention comprises the coating layer and the substrate layer, and the coating layer is formed on the substrate layer. The thickness of the entire functional panel is usually 2.5 mm or more. The upper limit of the overall thickness of the functional panel is not particularly limited, and the coating layer may be formed on both the surface and the back surface of the substrate layer, or may be disposed between the substrate layer and the coating layer as needed. A multilayer structure in which an intermediate layer composed of various materials is formed is formed. In this case, the coating layer is excellent in chemical resistance and dyeing resistance as described above, and it is preferred to form the coating layer as the outermost layer of the functional panel. The intermediate layer is, for example, an undercoat layer useful for improving the adhesion between the substrate layer and the coating layer, or a decorative layer having a pattern or color for improving the design of the functional panel.

The functional panel of the present invention obtained in this manner is formed with the above-mentioned specific coating layer at the substrate layer, and thus has excellent chemical resistance and dyeing resistance, even if it is strongly stimulated with acid or alkali. Sex cleaners are also less prone to deterioration or deterioration. Further, even if a dye such as a hair dye is used, discoloration or staining is less likely to occur. Thus, the functional panel of the present invention is suitable as a functional panel for a bathroom or kitchen, particularly in a dwelling.

Further, when the base material layer is made of an FRP containing an unsaturated polyester resin and glass fibers or carbon fibers, it is possible to further realize a functional panel having excellent durability, not only chemical resistance and dyeing resistance.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the examples.

Example: [Modulation of Photocurable Resin Composition]

According to the contents shown in Table 1, 60 parts by weight of a photopolymerizable oligomer and 40 parts by weight of a photopolymerizable monomer were added to and mixed with a stirring device, followed by addition of a photopolymerization initiator (IRGACURE 184, manufactured by Ciba Specialty Chemicals Inc.). 1 part by weight, stirred for 2 minutes, and subjected to a defoaming treatment, a photocurable resin composition (C1 to C11) was obtained.

[Example 1]

The photocurable resin composition C1 prepared above was applied to a thickness of 20 μm in the above-mentioned substrate of FRP (DECKMAT (registered trademark) 2415, manufactured by DIC Chemical Co., Ltd.). Next, UV (1000 mW/cm ² , 4000 mJ/cm ² ) was irradiated to harden the photocurable resin composition to obtain a functional panel.

[Examples 2 to 6]

A functional panel was obtained in accordance with Example 1 except that the photocurable resin compositions C2 to C6 prepared above were used, respectively.

[Comparative Examples 1 to 5]

A functional panel was obtained in accordance with Example 1 except that the photocurable resin compositions C7 to C11 prepared as described above were used, respectively.

(1) Determination of glass transition temperature

The measurement of the glass transition temperature (Tg) was carried out by using a dynamic viscoelastic device (DMS6100, manufactured by Seiko Instruments Inc.) under the conditions of a measurement frequency of 1.0 Hz and a temperature increase rate of 3.0 ° C/min.

(2) Evaluation of drug resistance

The functional panel obtained in Example 1 was immersed in each of the different conditions shown below, and the change of the functional panel was observed, and the degree of change was measured by a color difference meter (SpectroEye, SAKATA INX ENG. CO., LTD). The Lab color difference (ΔE) between the impregnated portion and the unimpregnated portion was determined by the following formula (A).

ΔE=(Δa ² +Δb ² +ΔL ² ) ^1/2 ‧‧‧‧‧‧‧(A)

The smaller the value, the better the resistance to the drug, preferably 3.0 or less, more preferably 1.0 or less. When it is 1.0 or less, it can be regarded as almost no change.

Further, a substrate composed of the above-mentioned FRP having no photocurable resin composition was used as Comparative Example 1, and the chemical resistance evaluation was performed in the same manner.

HCl‧‧‧‧ was immersed in a 3 mass% aqueous solution of HCl for 1 hour.

NaOH ‧ was immersed in a 5 mass % aqueous NaOH solution for 1 hour.

BM‧‧‧‧ was immersed in a commercially available detergent (Power Spray\Bath Magiclean (registered trademark), Kao Corporation) for 24 hours.

These results are shown in Table 2.

(3) Evaluation of dye resistance

The photocurable resin composition (C1 to C11) prepared above was applied to a glass substrate to a thickness of 1.0 mm. Each sample was obtained by irradiating UV (1000 mW/cm ² , 4000 mJ/cm ² ) under a nitrogen atmosphere to harden the photocurable resin composition.

The obtained sample was immersed in a commercially available hair dye (GATSBY returned to black hair (registered trademark): a mixture of 1 dose and 2 doses, manufactured by MANDOM Co., Ltd.) for 24 hours and washed with water, and the above (1) chemical resistance. In the same manner, the Lab color difference (ΔE) between the impregnated portion and the unimpregnated portion was determined by the above-described color difference meter according to the formula (A).

From the above results, it was found that the functional panel of the present invention can maintain good chemical resistance and exhibit excellent dyeing resistance. In particular, when a photopolymerizable single system is a low polarity such as isodecyl (meth) acrylate or dimethylol tricyclodecyl di(meth) acrylate, it is comparable to those of a highly polar one. Significantly reduce dye resistance.

Claims (4)

A functional panel comprising: a photopolymerizable monomer and a photopolymerizable oligomer having a dissolution parameter (SP value) of 17.0 (J/cm ³ ) of ^0.5 or more and 20.0 (J/cm ³ ) of ^0.5 or less a coating layer formed by curing the formed photocurable resin composition and having a glass transition temperature of 50 ° C or higher; and a substrate layer; wherein the photopolymerizable single system is a monomer represented by the following formula (1) (CH ₂ =CR ¹ COO) _n R ² ‧‧‧‧‧‧(1) (In the formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a carbon number of 5-20 The n-valent hydrocarbon group, n is an integer of 1 to 4). The functional panel of claim 1, wherein the photopolymerizable single system comprises isodecyl (meth) acrylate, 1,6-hexanediol di(meth) acrylate, dimethylol III Cyclodecyl di(meth) acrylate, isoamyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, isotetradecyl ( Methyl) acrylate, octadecyl (meth) acrylate, 3-methyl-1,5-pentanediol di(meth) acrylate, neopentyl glycol di(meth) acrylate, ring Hexane dimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate At least one monomer selected from the group. The functional panel of claim 1 or 2, wherein the photopolymerizable monomer and the photopolymerizable oligomer are formulated in an amount of 70:30 to 30:70 by mass. The functional panel of claim 1, wherein the substrate layer is composed of a material containing an unsaturated polyester resin, a filler, and glass fiber or carbon fiber.