TWI425060B - A photopolymerizable composition and a functional panel using the same - Google Patents

Description

Photopolymerizable composition and functional panel using the same

The present invention relates to a photopolymerizable composition which exhibits excellent compatibility with a low surface free energy compound, and more particularly to a functional panel which exerts particularly excellent antifouling properties by using the composition.

The functional panel which is a building material is a member which is disposed as a wall surface of a building, a floor surface, or a ceiling wall surface, and provides various functions such as sound insulation effect and humidity adjustment property depending on the position of the arrangement. In particular, when it is used as a member for a water use place such as a bathroom, a bathroom, or a kitchen in a house, the functional panel is required to have various characteristics such as antifouling property, water resistance, and moisture resistance which can withstand a more severe use environment. In particular, since the member for water use is exposed to moisture and moisture, chemical agents such as scale, mildew, detergent, and dyeing agent adhere to the surface, and dirt is likely to be generated.

In response to such fouling, it has been attempted to apply a composition having a low surface free energy compound having a small surface free energy to a surface having a reduced surface free energy to the member surface, thereby imparting good antifouling properties to the member. On the other hand, since the low surface free energy compound has poor compatibility with the coating composition, the composition may become cloudy and may not form a sufficiently hardened coating film, or the uniformity of the coating film may be impaired.

In this case, for example, Patent Document 1 discloses a coating cured product using a low surface free energy compound for improving the compatibility problem of a low surface free energy compound, which has a hardened phase with a coating material. A compatible group or a compatible segment or the like.

Prior art literature

Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2002-69378

However, as described above, if it is a low surface free energy compound having a compatible group or a compatible segment or the like which is compatible with the hardened material of the coating in the skeleton, a mixture of a highly polar portion and a low polar portion is formed. Molecular design within the backbone. In this case, if the blending amount of the low surface free energy compound is too small, the effect of lowering the surface free energy cannot be sufficiently obtained, and thus the antifouling property cannot be sufficiently exhibited. If the blending amount is too large, the cost is increased, and the coating film may be excessively exceeded. Excessive softening is required to impair the hard coatability of the resulting functional panel.

Further, as the composition of the cured product of the coating changes, the compatibility of the low surface free energy compound is also highly likely to change, which is difficult to carry out a free formulation.

Therefore, an object of the present invention is to provide a photopolymerizable composition and a functional panel using the same, wherein the photopolymerizable composition can be used in various formulations by using a formulation having a low surface free energy compound. When it is used for a coating layer of a functional panel, it exhibits characteristics such as chemical resistance and hot water resistance, and is particularly suitable as a member for a water-use site and exhibits an excellent antifouling effect.

In order to solve the above problems, the present inventors have found that a photopolymerizable composition which exhibits excellent compatibility and imparts excellent antifouling properties can be obtained by using a specific oligomer, a monomer, and a low surface free energy compound. The present invention has thus been completed.

That is, the photopolymerizable composition of the present invention is characterized by comprising:

(A) a low polarity (meth) acrylate oligomer having a poly(1,2-butylene oxide unit),

(B) a photopolymerizable monomer having a dissolution parameter (SP value) of 20.0 (J/cm ³ ) ^0.5 or less, and

(C) Low surface free energy compounds.

It is desirable that the low polarity (meth) acrylate oligomer (A) has a n-heptane tolerance of 0.5 g/10 g or more.

The photopolymerizable monomer (B) may be 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 an n-valent hydrocarbon group having 5 to 20 carbon atoms. n represents an integer of 1 to 4).

The aforementioned low surface free energy compound (C) may be a fluorine compound and/or a ruthenium compound.

It is preferable that the photopolymerizable composition has a mass of 0.1 to 5.0 with respect to 100 parts by mass of the total of the low-polarity (meth)acrylate oligomer (A) and the photopolymerizable monomer (B). The amount of the component contains the aforementioned low surface free energy compound (C).

The functional panel of the present invention is characterized by comprising a coating layer and a substrate layer, wherein the coating layer is obtained by curing the photopolymerizable composition.

The compatibility of the low surface free energy compound in the photopolymerizable composition of the present invention is extremely excellent, and by using the above composition as a coating layer, a functional panel excellent in antifouling property can be easily obtained. Such a good compatibility is independent of the type of the low surface free energy compound, and can be sufficiently maintained even if the amount of the compound is reduced, so that a free formulation can be ensured, and the cost can be reduced without impairing other physical properties such as hard coatability. .

The functional panel of the present invention comprising a coating layer composed of the above photopolymerizable composition is particularly suitable as a water-use member.

Hereinafter, the present invention will be described in detail.

The photopolymerizable composition of the present invention is characterized by comprising:

(A) a low polarity (meth) acrylate oligomer having a poly(1,2-butylene oxide unit),

(B) a photopolymerizable monomer having a dissolution parameter (SP value) of 20.0 (J/cm ³ ) ^0.5 or less, and

(C) Low surface free energy compounds.

[Low polarity (meth) acrylate oligomer (A)]

The photopolymerizable composition of the present invention contains a low polarity (meth) acrylate oligomer having a poly(1,2-butylene oxide unit). The low-polarity (meth) acrylate oligomer (A) is a low-polarity oligomer which exhibits high solubility to an organic solvent and is a poly(1,2-epoxy butyl hydride) represented by the following formula (i) An oligomer of an alkane unit.

[Chemical Formula 1]

In the above formula (i), m represents an integer of 1 to 200.

Further, in the case where the above low-polar (meth) acrylate oligomer (A) has a low polarity, specifically, it can be represented by a value of n-heptane tolerance, and the above value is preferably. It is 0.5 g/10 g or more, more preferably 0.7 g/10 g or more. Further, the n-heptane tolerance is a value obtained by holding 10 g of the resin at 25 ° C while adding n-heptane dropwise until white turbidity occurs, and the amount (g) of the n-heptane which can be added is an organic solvent. The indicator of solubility, the larger the value, the weaker the polarity.

Specific examples of the low-polarity (meth) acrylate oligomer (A) include a polyurethane-based (meth) acrylate oligomer and an epoxy (meth) acrylate oligomer. An ether-based (meth) acrylate oligomer, an ester-based (meth) acrylate oligomer, a polycarbonate-based (meth) acrylate oligomer, a fluorine-based (meth) acrylate oligomer, Polyoxymethylene (meth) acrylate oligomer or the like. These photopolymerizable oligomers can be synthesized by using polyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, bisphenol A type epoxy resin, phenol novolak type epoxy resin, polyol and The adduct of ε-caprolactone or the like is reacted with (meth)acrylic acid; or the polyisocyanate compound is amine-esterified with a (meth) acrylate compound having a hydroxyl group.

Among them, from the viewpoint of imparting suitable properties other than chemical resistance and dyeing resistance as a functional panel, a polyurethane-based (meth)acrylate oligomer is preferable, which is produced by using one or a plurality of reactive hydroxyl (OH group) butylene oxide modified polyols as a polyol, a polyurethane prepolymer synthesized from the polyol and a polyisocyanate, and a (meth) acrylate having a hydroxyl group added to the polyurethane prepolymer Or, the (meth) acrylate having an isocyanate group is added to the polyol. The low-polarity (meth) acrylate oligomer (A) may be any one of a monofunctional oligomer, a difunctional oligomer, and a polyfunctional oligomer, from the moderate degree of realization of the obtained photopolymerizable composition. From the viewpoint of crosslinking density, the number of functional groups is preferably 2 or more, more preferably 3 or more.

In addition, the number of the functional groups herein means the number of the above-mentioned functional groups of a plurality of molecules, and the average value is converted into a value of the number of functional groups in one molecule.

The above-mentioned butylene oxide-modified polyol used as the polyol is a polyether polyol obtained by adding 1,2-butylene oxide (BO) to a polyol in the presence of a basic catalyst. Further, a polyether polyol obtained by adding polyoxyalkylene such as propylene oxide (PO) to a poly(1,2-butylene oxide (BO)) may be added. In this case, the ratio of BO to other alkylene oxides is from 20:80 to 100:0, preferably from 50:50 to 100:0 in terms of a molar ratio. The GPC-based weight average molecular weight of these butylene oxide-modified polyols is usually from 100 to 15,000, preferably from 500 to 5,000.

As the above polyol, the above-mentioned butylene oxide-modified polyol may be used alone or in combination with other polyols. In this case, examples of the other polyhydric alcohol include a polyether polyol obtained by adding poly propylene oxide (PO), a polycarbonate polyol, a polybutadiene polyol, and a hydrogenated polybutadiene polyol. Acrylic polyol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, and the like. Further, the polyether polyol obtained by adding polybutylene oxide (BO) to the total amount of the polyol to be used is usually 20% by mass or more, preferably 50 to 100% by mass.

The polyisocyanate is not particularly limited as long as it has a plurality of isocyanate groups (NCO groups) in the molecule, and specific examples thereof include 2,4-toluene diisocyanate (2,4-TDI). 2,6-toluene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4 '-MDI), 1,4-phenylene diisocyanate, benzodimethyl diisocyanate (XDI), tetramethyl dimethyl diisocyanate (TMXDI), tolidine diisocyanate (TODI, tolidine diisocyanate), 1, Aromatic polyisocyanates such as 5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate Aliphatic polyisocyanate such as methyl ester (NBDI), trans cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), H ₁₂ MDI (hydrogenated MDI), H ₆ TDI (hydrogenated TDI) and alicyclic polyisocyanate compounds and the like diisocyanate; multi-polymethylene polyphenylene polyisocyanates and other polyisocyanate compounds; these isocyanuric Ester carbodiimide-modified polyisocyanate compound; these isocyanurate-modified isocyanates of the polyisocyanate compound and the like, may be used alone, or two or more may be used in combination.

In the synthesis of the above polyurethane prepolymer, a catalyst for an amine esterification reaction is preferably used. Examples of the catalyst for the esterification reaction include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, and tin octylate. , an organic tin compound such as monobutyltin oxide; an inorganic tin compound such as stannous chloride; an organic lead compound such as lead octenate; a cyclic amine such as triethylenediamine; p-toluenesulfonic acid, methanesulfonic acid, and fluorosulfuric acid Organic sulfonic acid; inorganic acid such as sulfuric acid, phosphoric acid, perchloric acid; alkali such as sodium alkoxide, lithium hydroxide, aluminum alcoholate, sodium hydroxide; tetrabutyl titanate, tetraethyl titanate, titanium a titanium compound such as tetraisopropyl acid; an oxime compound such as tris(2-ethylhexanoate) hydrazine; a quaternary ammonium salt; Among these catalysts, organotin compounds are preferred. These catalysts may be used alone or in combination of two or more. The amount of the above catalyst is preferably in the range of 0.001 to 1.0 part by mass based on 100 parts by mass of the above polyol.

Further, the above-mentioned (meth) acrylate having a hydroxyl group added to the polyurethane prepolymer has one or more hydroxyl groups and one or more (meth) acryloxy groups (CH ₂ =CHCOO- or CH ₂ =C) (CH ₃ )COO-) compound. The hydroxyl group-containing (meth) acrylate may be added to the isocyanate group of the above polyurethane prepolymer. Examples of the acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and pentaerythritol triacrylate. These hydroxy group-containing acrylates may be used alone or in combination of two or more.

The weight average molecular weight of the above-mentioned low polarity (meth) acrylate oligomer (A) based on GPC is usually from 400 to 100,000, preferably from 800 to 10,000.

When the above-mentioned low-polarity (meth) acrylate oligomer (A) is blended together with the photopolymerizable monomer (B) described later, the low surface free energy compound (C) can be extremely well compatible, and therefore When the obtained photopolymerizable composition is used, a functional panel which imparts excellent antifouling properties can be realized, and photopolymerization can be carried out in a short time by applying a photopolymerizable composition onto a substrate and performing light irradiation. When the composition is hardened, it is excellent in physical properties such as chemical resistance and dyeing resistance.

[Photopolymerizable monomer (B)]

The photopolymerizable composition of the present invention contains a photopolymerizable monomer (B) having a dissolution parameter (SP value) of 20.0 (J/cm ³ ) of ^0.5 or less. The SP value (δ) is generally defined by the following formula according to the Mohr evaporating energy (ΔEv) and the Moir volume (V) of the liquid.

SP value (δ) = (ΔEv / V) ^0.5

Further, according to the Fedors method, the SP value can be estimated only from the chemical structure (refer to "Solubility Parameter Values", Polymer Handbook, 4th Edition (J. Brandrup et al.)). Further, in the present specification, the SP value means a value calculated according to the Fedors method, and the lower the value, the weaker the polarity of the photopolymerizable monomer (B). The SP value of the photopolymerizable monomer (B) 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, and is usually 17.0 (J/cm ³ ) of ^0.5 or more.

In the case of the photopolymerizable monomer (B) exhibiting such an SP value, good compatibility with the above-mentioned low-polarity (meth) acrylate oligomer (A) can be maintained while effectively reducing the monomer itself. Has the polarity. In addition, since the photopolymerizable monomer (B) to be used has a low polarity, it is possible to greatly contribute to the improvement of the compatibility of the low surface free energy compound (C) described later, and it is presumed that the photopolymerizable composition thus obtained is obtained. When the coating layer is formed by hardening, the reactivity of the coating layer itself after curing can be sufficiently suppressed. In the functional panel of the present invention in which the above-mentioned coating layer is formed, since the low surface free energy compound (C) exhibits excellent compatibility, it is excellent in antifouling property, and can maintain good hot water resistance and can be expressed. Good chemical resistance and dyeing resistance, and will not react with detergents, dyes, etc. as necessary.

As the photopolymerizable monomer (B), it is preferred to use one or more propylene decyloxy groups (CH ₂ =CHCOO-) or methacryloxycarbonyl groups (CH ₂ =C(CH ₃ )COO-) ( The methyl acrylate monomer may be any one of a monofunctional monomer, a difunctional monomer, and a polyfunctional monomer.

Examples of the monofunctional monomer include isodecyl (meth)acrylate, decyl (meth)acrylate, tricyclodecyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. An alicyclic (meth)acrylic acid such as dicyclopentenyl acrylate or cyclohexyl (meth) acrylate; benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, (a) Base) propylene morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, (A) Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, (A) Tert-butyl acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, (A) Isooctyl acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate Monoalkyl ester, dodecyl (meth)acrylate , lauryl (meth)acrylate, octadecyl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, isostearyl (meth)acrylate, ( Tetrahydrofurfuryl methacrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyoxyethylene nonylphenyl ether acrylate, (methyl) Phenyloxyethyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy glycol (meth) acrylate, ethoxylate (meth) acrylate Ethyl ethyl ester, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethyl (meth) acrylate Aminoethyl ester, 7-amino-3,7-dimethyloctyl (meth) acrylate, ether skeleton (meth) acrylate, and the like.

Examples of the difunctional monomer include ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and di(methyl). ) 1,4-butanediol acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, di(meth)acrylic acid Neopentyl glycol ester, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dimethylol tricyclodecane Di(meth)acrylate of di(meth)acrylate, alkylene oxide addition diol of bisphenol A, di(meth)acrylate of alkylene oxide addition diol of hydrogenated bisphenol A An epoxy (meth) acrylate obtained by adding a (meth) acrylate to diglycidyl ether of bisphenol A.

Examples of the polyfunctional monomer include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxylated trimethylolpropane. Tris(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylic acid Ester, dipentaerythritol monohydroxypenta(meth)acrylate, and the like. These photopolymerizable monomers may be used singly or in combination of two or more.

Further, the SP value when two or more kinds of photopolymerizable monomers (B) are used means that the SP value of each monomer is multiplied by the respective mixing ratio (the ratio of each monomer when the total amount of monomers is 1) And add these to the value. For example, the photopolymerizable monomer having a SP value of 19.0 is 3/4 and the photopolymerizable monomer having an SP value of 21.0 is 1/4 of the total amount of the photopolymerizable monomer (B). In the meantime, the SP value of the entire photopolymerizable monomer (B) to be used is determined by the following formula (X).

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

Among the photopolymerizable monomers (B), 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 - in the group may be replaced by -CH=CH-. n represents an integer from 1 to 4.

That is, in the above formula (1), for example in the case of a chain, and unsaturated monomers, n = 1 R ² is an alkyl group having 5 to 20 carbon atoms, n = 2 R ² is 5 carbon atoms ~20 alkylene. Further, when it is a chain and is a saturated monomer, when n=3, R ² is a cyanide triyl group having 5 to 20 carbon atoms, and when n=4, it is a tetrasubstituted alkane having 5 to 20 carbon atoms. Alkane tetrayl. Examples of such R ^2, for example, _{-CH 2 CH 3, -CH 2 CH} 2 CH 3, -CH (CH 3) CH 3, cyclohexyl, cycloheptyl, cyclooctyl, nonyl, cyclodecyl group, etc. An alkylene group, an alkylene group such as -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )CH ₂ -, or the like, and a trisubstituted alkyl group represented by the following formula (2), as described below A tetrasubstituted alkyl group represented by the formula (3) or the like.

[Chemical Formula 2]

[Chemical Formula 3]

When the carbon number of R ² is less than 5, in the case of a chain hydrocarbon group, the SP value of the monomer tends to increase, and in the case of a cyclic hydrocarbon group, it becomes difficult to obtain itself. Further, when the carbon number of R ² exceeds 20, in the case of a cyclic hydrocarbon group, the resulting optical density of the crosslinking polymerizable composition tends to decrease. Assuming that the crosslink density is excessively lower than necessary, the dye such as a hair dye easily penetrates into the inside of the coating layer, so that the panel may be dyed.

Specific examples of the monomer represented by the above formula (1) include isodecyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, and dimethylol tricyclothracene. Alkyl di(meth)acrylate, isoamyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, (meth)acrylic acid Octadecyl ester, 3-methyl-1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate 1,9-nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate. Among them, preferred is 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, isodecyl (meth)acrylate, dimethylol tricyclohexane. The decane di(meth) acrylate is more preferably 1,9-nonanediol di(meth)acrylate or dimethylol tricyclodecane di(meth) acrylate. If it is such a monomer, since it has a more suitable SP value, it has a tendency to show favorable low polarity, and it can not only improve the anti-fouling property of the obtained functional panel, but also can improve chemical-resistance and dye-resistance further. Further, the function as the reactive diluent of the above-mentioned low-polarity (meth) acrylate oligomer (A) can also be effectively exhibited.

Further, the photopolymerizable monomer (B) has a functional group number of usually 1 to 6, preferably 1 to 4. In addition, when the number of functional groups is 1, the crosslinking density tends to increase, and when the number of functional groups is from 2 to 6, preferably from 2 to 4, the crosslinking reaction tends to be suitably maintained in the photopolymerizable composition. It is presumed that it is particularly easy to effectively suppress the phenomenon that the dye penetrates into the inside of the coating layer to dye the panel. Therefore, in this case, not only good antifouling properties can be obtained, but also a functional panel in which a coating layer having suitable curability is formed can be obtained while effectively maintaining chemical resistance and dyeing resistance.

[Low surface free energy compound (C)]

The photopolymerizable composition of the present invention contains a low surface free energy compound (C). The low surface free energy compound (C) is a compound having a low surface free energy, and by containing the compound, the wettability of the photopolymerizable composition can be lowered, and the coating formed of the above composition can be formed on the substrate. The layer can increase the water contact angle, thereby suppressing the adhesion of various kinds of dirt represented by scale, and improving the antifouling property of the functional panel.

The low surface free energy compound (C) is, for example, a fluorine compound or a ruthenium compound, and these may be used alone or in combination of two or more. Examples of the fluorine compound, specifically, desirably, selected from the group consisting of having _{-CF 3, -CF 2 H, -CF} 2 2 CF - compound and -CF _{2 CFH-} group consisting of at least one skeleton. Moreover, these skeletons are more suitable as they are closer to the latter. As a commercially available fluorine compound, MODIPER F200 (manufactured by Nippon Oil Co., Ltd.), OPTOOL DAC (manufactured by DAIKIN INDUSTRIES, LTD.), or the like can be used.

Specifically, the ruthenium compound is preferably a compound having a dimethyl siloxane skeleton represented by the following formula (ii).

[Chemical Formula 4]

In the above formula (ii), q represents an integer of 1 to 200. As the ruthenium compound, commercially available eucalyptus oil such as SILAPLANE (manufactured by ChisSO CORPORATION) or dimethyl eucalyptus oil (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

[Photopolymerizable composition]

The photopolymerizable composition used in the functional panel of the present invention contains a low polarity (meth) acrylate oligomer (A), a photopolymerizable monomer (B), and a low surface free energy compound (C). The amount of the low-polarity (meth) acrylate oligomer (A) to the photopolymerizable monomer (B) is usually 80:20 to 20:80 by mass ratio, preferably 30:70. The amount of 70:30. When the amount of the monomer is too small, the viscosity of the obtained photopolymerizable composition may increase, and the coatability may be deteriorated, and physical properties such as chemical resistance and dyeing resistance may not be sufficiently ensured. In addition, when the amount of the monomer is too large, the flexibility of the coating film is lowered and the brittleness tends to be high. Therefore, when the amount of the low-polarity (meth) acrylate oligomer (A) and the photopolymerizable monomer (B) is within the above range, the photopolymerizable monomer (B) can be sufficiently exhibited. Polarity, therefore, the chemical resistance and dyeing resistance of the functional panel can be improved by these SP values, and the excellent compatibility of the low surface free energy compound (C) can be ensured, and good antifouling can be exerted. Sex. Further, the photopolymerizable monomer (B) functions as an effective diluent for the low-polarity (meth)acrylate oligomer (A), and the photopolymerizable composition is likely to exhibit an appropriate viscosity and can be imparted well. Coating properties.

In addition, the amount of the low surface free energy compound (C) is usually 0.1 to 5.0 based on 100 parts by mass of the total of the low polarity (meth) acrylate oligomer (A) and the photopolymerizable monomer (B). The amount of the mass fraction is preferably from 0.1 to 4.0 parts by mass, more preferably from 0.1 to 3.0 parts by mass. When the amount of the low surface free energy compound (C) is less than 0.1 part by mass, sufficient antifouling property may not be achieved, and when it exceeds 5.0 parts by mass, the coating film may excessively soften beyond the desired functional panel. The amount of the compound which is hard-coating and which cannot sufficiently ensure compatibility is likely to increase.

In addition, the photopolymerizable composition may further contain, in addition to the photopolymerizable monomer (B) having a predetermined SP value, in addition to the above-described light, without departing from the effects of the present invention. A monomer other than the polymerizable monomer (B). In other words, when the other monomer is blended, the SP value calculated from the SP value of the other monomer based on the above formula (X) may be within the range of the SP value.

A well-known photopolymerization initiator can be used for the said photopolymerizable composition. This photopolymerization initiator causes the polymerization of the above-mentioned low-polarity (meth)acrylate oligomer (A) and the photopolymerizable monomer (B) by irradiation of ultraviolet rays. Specific examples of the photopolymerization initiator include 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, and 2,2-dimethoxy-2-phenyl group. Acetophenone, acetophenone diethyl ketal, alkoxyacetophenone, benzoin dimethyl ketal, benzophenone and 3,3-dimethyl-4-methoxybiphenyl a benzophenone derivative such as a ketone, 4,4-dimethoxybenzophenone or 4,4-diaminobenzophenone, an alkyl benzoyl benzoate or a bis(4-dioxane) Benzoin derivatives such as phenylamino phenyl) ketone, benzophenone and benzoin methyl ketal, benzoin derivatives such as benzoin and benzoin isobutyl ether, benzoin isopropyl Ether, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, xanthone, thioxanthone and thioxanthone derivatives, hydrazine, 2,4,6-trimethylbenzimidazole Diphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzene Mercapto)-phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1,2-benzyl-2-dimethylamino- 1-(morpholinophenyl)-butanone-1 and the like. These photopolymerization initiators may be used alone or in combination of two or more. It is preferable that the photopolymerization initiator in the photopolymerizable composition is blended with respect to 100 parts by mass of the total of the low-polarity (meth)acrylate oligomer (A) and the photopolymerizable monomer (B). The amount is in the range of 0.1 to 10 parts by mass. When the amount of the photopolymerization initiator is less than 0.1 part by mass, the effect of initiating the polymerization reaction is small. On the other hand, when it exceeds 10 parts by mass, the effect of initiating the polymerization reaction is saturated, and the cost of the raw material increases.

In addition, the photopolymerizable composition may further contain a photosensitizer as needed in consideration of the required curing reactivity, stability, and the like. The photosensitizer has a function of absorbing energy by being irradiated with light, and the energy or electrons are moved into a polymerization initiator to initiate polymerization. Examples of the photosensitizer include p-amylaminobenzoic acid isoamyl ester and the like. It is preferable that the amount of these photosensitizers is in the range of 0.1 to 10 parts by mass based on 100 parts by mass of the total of the low-polarity (meth)acrylate oligomer (A) and the photopolymerizable monomer (B). The amount.

Furthermore, in the photopolymerizable composition, a polymerization inhibitor may be further contained as needed in consideration of the required curing reactivity, stability, and the like. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, and 2,6-di-tert-butyl-p-cresol. Butylhydroxyanisole, 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, 2,5-dihydroxy-p-quinone, and the like. It is preferable that the amount of these polymerization inhibitors is 0.1 to 10 parts by mass based on 100 parts by mass of the total of the low-polarity (meth)acrylate oligomer (A) and the photopolymerizable monomer (B). The amount of range.

In addition, the photopolymerizable composition used for the formation of the coating layer may contain an organic solvent such as an ether, a ketone or an ester as a diluent solvent, and examples of the organic solvent include propylene glycol monomethyl ether acetate (PMA) and methyl ethyl ketone. (MEK), methyl isobutyl ketone (MIBK), acetone, or butyl lactate. These diluent solvents may be used alone or in combination of two or more.

As described above, the photopolymerizable composition is used as a coating liquid as needed, and is applied to a surface of a substrate. The coating method may be a known method, and examples thereof include a gravure coating method, a roll coating method, a reverse coating method, a knife coating method, and a die coating method (die). Coating), lip coating, doctor coating, extrusion coating, slide coating, bar coating, curtain coating ), extrusion coating method, spin coating method, and the like.

[coating layer]

The photopolymerizable composition is applied onto a substrate, and then photocured to form a coating layer on the substrate layer. As a method of hardening the light, there is generally a method of irradiating ultraviolet rays. The surface on the base material layer for forming the coating layer may be only one of the front surface and the back surface, or may be double-sided, and may be appropriately selected as necessary. Further, when the amount of irradiation of the light when the photopolymerizable composition is cured, when ultraviolet rays are used, the irradiation intensity is usually 20 to 2000 mW/cm ² and the irradiation amount is 100 to 5000 mJ/cm ² , whereby the light is emitted. The polymerizable composition usually hardens in a few seconds to several tens of seconds. Since it can be hardened in a short time in this way, the productivity of the obtained functional panel can be improved.

The thickness of the coating layer can be appropriately selected depending on the desired pattern and chemical resistance, and is not particularly limited, and is usually expected to be in the range of 1 μm to 200 μm.

Further, in the case of irradiating ultraviolet rays, since the ultraviolet curing reaction is a radical reaction, it is easily blocked by oxygen. Therefore, after the photocurable composition is applied to the substrate, the composition is cured in a nitrogen atmosphere in order to avoid contact with oxygen.

Further, from the viewpoint of sufficiently ensuring good antifouling properties, the surface free energy of the coating layer formed by photocuring is usually 12 to 30 mJ/m ² .

[Substrate layer]

Examples of the material of the base material layer used in the functional panel of the present invention include inorganic materials such as slate, concrete, metal, calcium silicate, calcium carbonate, and glass; wood materials, and polypropylene and polyphenylene. Organic materials such as ethylene, polycarbonate, and unsaturated polyester resins; and composite materials thereof. Among them, a material obtained by adding a fiber such as glass fiber or carbon fiber to an organic agent is a so-called FRP (fiber reinforced plastic). Examples of the FRP include a sheet-like sheet molding compound (SMC) containing an unsaturated polyester resin, a filler, and glass fibers or carbon fibers, and is a composite material similar to SMC and comprising a short fiber. BMC (bulk molding compound) and the like. In general, FRP is compounded with a thermosetting resin, an organic peroxide (hardener), a filler, a low shrinkage agent, an internal mold release agent, a reinforcing material, a crosslinking agent, and a tackifier. The mold set to a predetermined temperature is pressurized and molded into a shape suitable as a position where the building material is placed. In addition, as long as it is an FRP containing an unsaturated polyester which is a thermoplastic resin, a filler, and a glass fiber or a carbon fiber as a reinforcing material, the strength, durability, and the like of the entire functional panel can be further improved.

As the unsaturated polyester, an unsaturated acid of a polybasic acid such as maleic anhydride or fumaric acid may be used together with ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, or trimethyl pentanediol. A polyol such as neopentyl glycol, trimethylpropane monoallyl ether, hydrogenated bisphenol or bisphenol dioxypropyl ether is produced.

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

As the glass fiber and the carbon fiber as the reinforcing material, a fiber having a fiber length of about 20 to 50 mm and a fiber diameter of about 5 to 25 μm can be suitably used, and it is preferably contained in an amount of 10 to 70% by mass in the FRP. The FRP used as the above-mentioned base material layer can be produced by mixing these components, and forming an FRP having a predetermined thickness and size by an FRP production apparatus or the like.

Further, the thickness of the base material layer may vary depending on the use of the functional panel, and 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 above coating layer and a substrate layer, and the coating layer is formed on the substrate layer. The thickness of the functional panel as a whole is usually preferably 2.5 mm or more. The upper limit of the thickness of the functional panel as a whole is not particularly limited, and the coating layer may be formed on both the front and back surfaces of the substrate layer, or may be formed between the layers in addition to the substrate layer and the coating layer as needed. There is a multilayer structure of an intermediate layer formed of various materials. In this case, as described above, the coating layer exhibits not only excellent antifouling properties but also chemical resistance and dyeing resistance. Therefore, it is preferable to form the coating layer as the outermost layer of the functional panel. Examples of the intermediate layer include an undercoat layer for improving the adhesion between the base layer and the coating layer, and a decorative layer for imparting a pattern or a color to improve the pattern of the functional panel.

Since the functional layer of the present invention thus obtained has the specific coating layer formed on the base material layer, it exhibits excellent antifouling properties, and is excellent in hot water resistance, chemical resistance, and dyeing resistance, and can be effectively suppressed. The adhesion of various kinds of dirt represented by the scale is not easily deteriorated or deteriorated even if a highly irritating detergent containing an acid or a base is used. Further, even if a dye such as a hair dye is used, discoloration and staining are unlikely to occur. Therefore, the functional panel of the present invention is particularly suitable as a functional panel disposed in a bathroom or kitchen in a house.

Further, if FRP comprising an unsaturated polyester resin and glass fibers or carbon fibers is used as the substrate layer, the following functional panel can be realized: not only excellent antifouling properties, chemical resistance, and dyeing resistance are imparted. It also gives excellent durability.

(Example)

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

[Production Example 1: Preparation of oligomer (a)]

Using a potassium hydroxide as a catalyst, 6 mol of ethylene oxide was added to 1 mol of glycerin (manufactured by Kanto Chemical Co., Ltd.) at a reaction temperature of 110 ° C to obtain a polyhydric alcohol. The above polyol and 3 mol of 2,4-toluene diisocyanate were placed in a reaction vessel equipped with a nitrogen introduction tube, a stirrer and a condenser, and reacted at 70 ° C for 2 hours.

Next, 6 mol of 2-hydroxyethyl acrylate and a trace amount of dibutyltin dilaurate as a catalyst were slowly added, and further reacted at 70 ° C for 15 hours to obtain a polyurethane acrylate having a polyethylene oxide unit having a weight average molecular weight of about 1300. Oligomer (a).

[Production Example 2: Preparation of oligomer (b)]

Using a potassium hydroxide as a catalyst, 6 mol of propylene oxide was added to 1 mol of glycerin (manufactured by Kanto Chemical Co., Ltd.) at a reaction temperature of 110 ° C to obtain a polyhydric alcohol. The above polyol and 3 mol of 2,4-toluene diisocyanate were placed in a reaction vessel equipped with a nitrogen introduction tube, a stirrer and a condenser, and reacted at 70 ° C for 2 hours.

Next, 6 mol of 2-hydroxyethyl acrylate and a trace amount of dibutyltin dilaurate as a catalyst were slowly added, and further reacted at 70 ° C for 15 hours to obtain a polyurethane ester acrylate having a polypropylene oxide unit having a weight average molecular weight of about 1300. Polymer (b).

[Production Example 3: Preparation of oligomer (c)]

1 mol of CaPa3050 (manufactured by PERSTORP) and 3 mol of 2,4-toluene diisocyanate were added to a reaction vessel equipped with a nitrogen introduction tube, a stirrer and a condenser, and reacted at 70 ° C for 2 hours.

Next, 6 mol of 2-hydroxyethyl acrylate and a trace amount of dibutyltin dilaurate as a catalyst were slowly added, and further reacted at 70 ° C for 15 hours to obtain a polyurethane acrylate oligomer having an ester skeleton having a weight average molecular weight of about 1400 ( c).

[Production Example 4: Preparation of oligomer (d)]

Using a potassium hydroxide as a catalyst, 12 mol of butylene oxide was added to 1 mol of propylene glycol (manufactured by Kanto Chemical Co., Ltd.) at a reaction temperature of 110 ° C to obtain a polyhydric alcohol. The above polyol and 2 mol of 2,4-toluene diisocyanate were placed in a reaction vessel equipped with a nitrogen introduction tube, a stirrer and a condenser, and reacted at 70 ° C for 2 hours.

Next, 4 mol of 2-hydroxyethyl acrylate and a trace amount of dibutyltin dilaurate as a catalyst were slowly added, and further reacted at 70 ° C for 15 hours to obtain a polyurethane ester acrylate having a weight average molecular weight of about 1500 and having a butylene oxide unit. Polymer (x).

Polyol was obtained by adding 4 mol of butylene oxide to 1 mol of pentaerythritol (manufactured by Kanto Chemical Co., Ltd.) at a reaction temperature of 110 ° C using potassium hydroxide as a catalyst. The above polyol and 4 mol of 2,4-toluene diisocyanate were placed in a reaction vessel equipped with a nitrogen introduction tube, a stirrer and a condenser, and reacted at 70 ° C for 2 hours.

Next, 8 mol of 2-hydroxyethyl acrylate and a trace amount of dibutyltin dilaurate as a catalyst were slowly added, and further reacted at 70 ° C for 15 hours to obtain a polyurethane ester acrylate having a weight average molecular weight of about 1500 and having a butylene oxide unit. Polymer (y).

The above-mentioned polyurethane acrylate oligomer (x) and the polyurethane acrylate oligomer (y) are mixed in such a manner that the ratio of the acrylic functional group is 50:50, and the average functional group number 3 and the weight average molecular weight of about 1500 are obtained. A polyurethane (meth) acrylate oligomer (d) of a 1,2-butylene oxide unit.

[Production Example 5: Preparation of oligomer (e)]

Polyol was obtained by adding 8 mol of butylene oxide to 1 mol of propylene glycol (manufactured by Kanto Chemical Co., Ltd.) at a reaction temperature of 110 ° C using potassium hydroxide as a catalyst. The above polyol and 2 mol of 2,4-toluene diisocyanate were placed in a reaction vessel equipped with a nitrogen introduction tube, a stirrer and a condenser, and reacted at 70 ° C for 2 hours.

Next, 4 mol of pentaerythritol triacrylate and a trace amount of dibutyltin dilaurate as a catalyst were slowly added, and further reacted at 70 ° C for 15 hours to obtain a polyurethane having a poly(1,2-butylene oxide unit) having a weight average molecular weight of about 1600. Acrylate oligomer (e).

For each of the obtained oligomers, the n-heptane tolerance was measured in accordance with the method shown below. The results are shown in Table 1.

<<Determination of n-heptane tolerance>>

10 g of each of the oligomers was kept at 25 ° C, and n-heptane was added dropwise thereto, and the addition was continued until white turbidity occurred, and the value (g: g/10 g) of the amount of n-heptane at this time (unit: g/10 g) was measured.

[Examples 1 to 3, Comparative Examples 1 to 5]

According to the blending amounts shown in Tables 2 to 3, various oligomers and photopolymerizable monomers are added to the stirring device, mixed, and a low surface free energy compound is further added, followed by 1 part by mass of a photopolymerization initiator (IRGACURE 184, The product of Ciba Specialty Chemicals Inc. was stirred for 2 minutes, and defoaming treatment was carried out to obtain each photopolymerizable composition.

Using the obtained photopolymerizable composition, the compatibility of the low surface free energy compound (C) in the composition was evaluated according to the following method. The results are shown in Tables 2 to 3.

<<Compatibility evaluation>>

The obtained photopolymerizable composition was visually judged to exhibit good compatibility, and the evaluation for transparency was ○, and the evaluation of white turbidity or layer separation was marked as ×.

*1: Fluorine compound, MODIPER F200 (made by Nippon Oil Co., Ltd.)

*2: 矽 compound, manufactured by TSF4452, Momentive Performance Materials Japan LLC

*3: Fluorine compound, OPTOOL DAC (manufactured by DAIKIN INDUSTRIES, LTD.)

*4: 矽 compound, SILAPLANE FM7725 (manufactured by CHISSO CORPORATION)

*5: The amount of the mixture with respect to 100 parts by mass of the total of the oligomer and the monomer

*6: 1,9-nonanediol acrylate (manufactured by Kyoeisha Chemical Co., Ltd.), SP value = 19.2 (J/cm ³ ) ^0.5

*7: Trimethylolpropane triacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), SP value = 20.2 (J/cm ³ ) ^0.5

*8: Acrylhydrazine morpholine (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Sp value = 25.0 (J/cm ³ ) ^0.5

*9: Dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), SP value = 18.7 (J/cm ³ ) ^0.5

According to the above results, it is understood that in Examples 1 to 3 in which the low-polarity (meth)acrylate oligomer (A) and the photopolymerizable monomer (B) are blended, any low surface free energy compound (C) is blended. In the case of excellent compatibility, the properties can be maintained even if the amount is reduced.

Claims (4)

A photopolymerizable composition comprising: (A) a low polarity (meth) acrylate oligomer having a poly(1,2-butylene oxide unit); (B) a dissolution parameter (Sp value) of 20.0 (J/cm ³ ) a photopolymerizable monomer of ^0.5 or less; and (C) a low surface free energy compound; the n-heptane tolerance of the low polarity (meth) acrylate oligomer (A) is 0.5 g / 10 g or more; the low surface free energy compound (C) is a fluorine compound and/or a hydrazine compound. The photopolymerizable composition according to claim 1, wherein the photopolymerizable monomer (B) 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, R ² represents an n-valent hydrocarbon group having 5 to 20 carbon atoms, and n represents an integer of 1 to 4). The photopolymerizable composition according to claim 1 or 2, wherein the total amount of the low-polarity (meth)acrylate oligomer (A) and the photopolymerizable monomer (B) is 100 parts by mass, The low surface free energy compound (C) is contained in an amount of 0.1 to 5.0 parts by mass. A functional panel comprising a coating layer and a substrate layer, wherein the coating layer is cured by curing the photopolymerizable composition according to any one of claims 1 to 3.