JP5543808B2 - Photopolymerizable composition and functional panel using the same - Google Patents

Description

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

  Functional panels as building materials are members that are placed as building walls, floors, or ceiling walls. Depending on where they are placed, various functions such as soundproofing and humidity control are added. Has been. Such functional panels, particularly when used as watering parts in bathrooms, washrooms, kitchens, etc. in houses, can withstand even the harsher usage environments, such as antifouling, water resistance, moisture resistance, etc. It is required to have the following characteristics. In particular, since the water circulating member is exposed to moisture or moisture, chemicals such as scales, molds, cleaning agents, and dyeing agents adhere to the members, and stains easily occur.

  By applying a low surface free energy compound having a low surface free energy to such stains, a composition having a reduced surface free energy is applied to the surface of the member to give good antifouling properties to the member. It has been tried. On the other hand, since the low surface free energy compound has poor compatibility with the coating composition, the composition becomes cloudy and cannot form a sufficiently cured coating film, or the coating film uniformity is low. It may be damaged.

  Under these circumstances, for example, in Patent Document 1, a paint using a low surface free energy compound having a compatible group or a compatible segment or the like with a paint cured product in order to improve the compatibility problem of the low surface free energy compound. A cured product is disclosed.

JP 2002-69378 A

However, as described above, a low surface free energy compound having a compatible group or compatible segment with a cured paint in its skeleton, as described above, a molecular design in which a high polarity site and a low polarity site are mixed in the skeleton It becomes. In such a case, if the blending amount of the low surface free energy compound is too small, the effect of reducing the surface free energy cannot be obtained sufficiently, so that the antifouling property cannot be sufficiently exhibited, and if the blending amount is too large, the cost is high. In addition, the hard coat property of the functional panel obtained by softening the coating more than necessary may be impaired.
In addition, the compatibility of the low surface free energy compound is highly likely to change greatly as the composition of the cured paint is changed, and free formulation design is difficult.

  Therefore, the present invention employs a compound having excellent compatibility with the low surface free energy compound, thereby enabling the use of a wide variety of low surface free energy compounds, and when used in the coating layer of the functional panel. Provided are a photopolymerizable composition capable of exhibiting an excellent antifouling effect, which is particularly suitable as a watering member, in addition to characteristics such as chemical properties and hot water resistance, and a functional panel using the same. The purpose is that.

  In order to solve the above-mentioned problems, the present inventor uses a specific oligomer, monomer, and low surface free energy compound to exhibit excellent compatibility and impart good antifouling property. Has been found, and the present invention has been completed.

［式（ｉ）中、ｍは１〜２００の整数を示す］で表される１，２−ポリブチレンオキサイド単位を有し、ｎ−ヘプタントレランスが０．５ｇ／１０ｇ以上である（メタ）アクリレートオリゴマーと、
（Ｂ）溶解パラメーター（ＳＰ値）が２０．０(Ｊ／ｃｍ³)^0.5以下であり、下記式（１）：
（ＣＨ ₂ ＝ＣＲ ¹ ＣＯＯ） _n Ｒ ² ・・・・・（１）
［式（１）中、Ｒ ¹ は水素原子またはメチル基を示し、Ｒ ² は炭素数５〜２０のｎ価の炭化水素基を示し、ｎは１〜４の整数を示す］で表される光重合性モノマーと、
（Ｃ）フッ素化合物および／またはケイ素化合物
とを含有し、
前記（メタ）アクリレートオリゴマー（Ａ）と前記光重合性モノマー（Ｂ）との合計１００質量部に対し、前記フッ素化合物および／またはケイ素化合物（Ｃ）を０．１〜５．０質量部の量で含有することを特徴とする。 That is, the photopolymerizable composition of the present invention is
(A) The following formula (i):

Wherein (i), m represents an integer of 1 to 200] have a 1,2-polybutylene oxide unit represented by is n- heptane tolerance 0.5 g / 10 g or more (meth) acrylate An oligomer,
(B) solubility parameter (SP value) Ri der 20.0 (J / cm ^{3) 0.5} or less, the following equation (1):
(CH ₂ = CR ¹ COO) _n R ² (1)
[In 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, n is an integer of 1-4] you express in A photopolymerizable monomer;
(C) a fluorine compound and / or a silicon compound ,
0.1 to 5.0 parts by mass of the fluorine compound and / or silicon compound (C) with respect to a total of 100 parts by mass of the (meth) acrylate oligomer (A) and the photopolymerizable monomer (B). It is characterized by containing.

  The functional panel of the present invention is characterized by comprising a coating layer formed by curing the photopolymerizable composition and a base material layer.

The photopolymerizable composition of the present invention has extremely good compatibility of the fluorine compound and / or silicon compound , and a functional panel having excellent antifouling properties can be easily obtained by using such a composition as a coating layer. be able to. Such good compatibility can be maintained sufficiently regardless of the type of fluorine compound and / or silicon compound, and even if the blending amount is reduced. Cost reduction can be realized without impairing other physical properties.
The functional panel of the present invention including the coating layer made of the photopolymerizable composition is particularly suitable as a water-circulating member.

Hereinafter, the present invention will be described in detail.
The photopolymerizable composition of the present invention comprises
(A) have a 1,2-polybutylene oxide unit represented by the above formula (i), and is (meth) acrylate oligomer in n- heptane tolerance 0.5 g / 10 g or more,
(B) solubility parameter (SP value) Ri der 20.0 (J / cm ^{3) 0.5} or less, a photopolymerizable monomer you express the above formula (1),
(C) a fluorine compound and / or a silicon compound ,
0.1 to 5.0 parts by mass of the fluorine compound and / or silicon compound (C) with respect to a total of 100 parts by mass of the (meth) acrylate oligomer (A) and the photopolymerizable monomer (B). It is characterized by containing.

[ (Meth) acrylate oligomer (A)]
The photopolymerizable composition of the present invention contains a ( meth) acrylate oligomer having 1,2-polybutylene oxide units. The ( meth) acrylate oligomer (A) is a low-polarity oligomer, shows high solubility in an organic solvent, and is an oligomer having a 1,2-polybutylene oxide unit represented by the above formula (i). . In said formula (i), m shows the integer of 1-200.

Further, that the above (meth) acrylate oligomer (A) is a low polarity, specifically, can be represented by the value of n- heptane tolerance, such value is 0.5 g / 10 g or more, preferably 0. It is 7 g / 10 g or more. In addition, n-heptane tolerance means the value of the amount (g) of n-heptane that can be added until n-heptane is dropped into the resin 10 g while keeping 10 g of the resin at 25 ° C., and is organic. It becomes an index of solubility in a solvent, and the larger the value, the lower the polarity.

  Specific examples of the low polarity (meth) acrylate oligomer (A) include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, ether (meth) acrylate oligomers, and ester (meth). Examples include acrylate oligomers, polycarbonate-based (meth) acrylate oligomers, fluorine-based (meth) acrylate oligomers, and silicone-based (meth) acrylate oligomers. These photopolymerizable oligomers include polyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, bisphenol A type epoxy resin, phenol novolac type epoxy resin, adducts of polyhydric alcohol and ε-caprolactone, and (meth) acrylic. It can be synthesized by reaction with an acid or by urethanizing a polyisocyanate compound and a (meth) acrylate compound having a hydroxyl group.

Among these, from the viewpoint of imparting suitable properties other than chemical resistance and dyeing resistance as a functional panel, urethane (meth) acrylate oligomers are preferable, which include one active hydrogen group (OH group) as a polyol or A plurality of butylene oxide-modified polyols are used, a urethane prepolymer is synthesized from the polyol and polyisocyanate, and a hydroxyl group-containing (meth) acrylate is added to the urethane prepolymer, or the polyol has an isocyanate group. It is manufactured by adding (meth) acrylate. The low polarity (meth) acrylate oligomer (A) may be a monofunctional oligomer, a bifunctional oligomer, or a polyfunctional oligomer, but from the viewpoint of realizing an appropriate crosslinking density of the resulting photopolymerizable composition. The number of functional groups is preferably 2 or more, and more preferably 3 or more.
In addition, the number of functional groups means here the value which calculated | required the number of the said functional groups from several molecules, and averaged these and converted it as the number of the functional groups which have in 1 molecule.

  The butylene oxide-modified polyol used as the polyol is a polyether polyol obtained by addition polymerization of 1,2-butylene oxide (BO) to a polyhydric alcohol in the presence of an alkali catalyst. Further, it may be a polyether polyol obtained by addition polymerization of not only 1,2-butylene oxide (BO) but also other alkylene oxides such as propylene oxide (PO). In this case, the ratio of BO to other alkylene oxide is 20:80 to 100: 0, preferably 50:50 to 100: 0, in terms of molar ratio. The weight average molecular weight of these butylene oxide-modified polyols by GPC is usually 100 to 15,000, preferably 500 to 5,000.

  As the polyol, the butylene oxide-modified polyol may be used alone or in combination with other polyols. In this case, as other polyols, for example, polyether polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, acrylic polyol, ethylene glycol, diethylene glycol, propylene glycol, obtained by addition polymerization of propylene oxide (PO), Examples include dipropylene glycol, butanediol, pentanediol, and hexanediol. In addition, it is desirable that the polyether polyol obtained by addition polymerization of butylene oxide (BO) is usually 20% by mass or more, preferably 50 to 100% by mass in the total amount of polyol used.

The polyisocyanate is not particularly limited as long as it is a compound having a plurality of isocyanate groups (NCO groups) in the molecule. Specific examples thereof include 2,4-tolylene diisocyanate (2,4-TDI), 2, 6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene Aromatic polyisocyanates such as diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene Gii Aliphatic polyisocyanates such as socyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate methyl (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), H ₁₂ MDI Diisocyanate compounds such as alicyclic polyisocyanates such as (hydrogenated MDI) and H ₆ TDI (hydrogenated TDI); polyisocyanate compounds such as polymethylene polyphenylene polyisocyanate; carbodiimide-modified polyisocyanates of these isocyanate compounds; these isocyanates Examples of the compound include isocyanurate-modified polyisocyanate, and the compound may be used alone or in combination of two or more.

  In the synthesis of the urethane prepolymer, it is preferable to use a catalyst for urethanization reaction. Examples of the catalyst for urethanization reaction include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin thiocarboxylate, tin octenoate, monobutyltin oxide and the like; stannous chloride, etc. Inorganic lead compounds; organic lead compounds such as lead octenoate; cyclic amines such as triethylenediamine; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, fluorosulfuric acid; sulfuric acid, phosphoric acid, perchloric acid, etc. Inorganic acids; bases such as sodium alcoholate, lithium hydroxide, aluminum alcoholate and sodium hydroxide; titanium compounds such as tetrabutyl titanate, tetraethyl titanate and tetraisopropyl titanate; bismuth tris (2-ethylhexanoate) And bismuth compounds such as quaternary ammonium salts. Of these catalysts, organotin compounds are preferred. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is preferably in the range of 0.001 to 1.0 part by mass with respect to 100 parts by mass of the polyol.

The (meth) acrylate having a hydroxyl group to be added to the urethane prepolymer has one or more hydroxyl groups and is a (meth) acryloyloxy group (CH ₂ ═CHCOO— or CH ₂ ═C (CH ₃ ) COO—). Is a compound having one or more. The (meth) acrylate having a hydroxyl group can be added to the isocyanate group of the urethane prepolymer. Examples of the acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and pentaerythritol triacrylate. These acrylates having a hydroxyl group may be used alone or in combination of two or more.

  The low-polarity (meth) acrylate oligomer (A) has a weight average molecular weight by GPC of usually 400 to 100,000, preferably 800 to 10,000.

Such (meth) acrylate oligomer (A), if formulated with later-described photopolymerizable monomer (B), since the fluorine compound and / or a silicon compound (C) very well may be compatible, By using the resulting photopolymerizable composition, it is possible to realize a functional panel imparted with excellent antifouling properties, and it is short only by applying the photopolymerizable composition on a substrate and irradiating it with light. It can be cured in time, and can exhibit excellent effects in physical properties such as chemical resistance and dye resistance.

[Photopolymerizable monomer (B)]
The photopolymerizable composition of the present invention contains a photopolymerizable monomer (B) having a solubility parameter (SP value) of 20.0 (J / cm ³ ) ^0.5 or less. The SP value (δ) is generally defined by the following equation from the molar evaporation energy (ΔEv) and the molar volume (V) of the liquid.
SP value (δ) = (δEv / V) ^0.5
Furthermore, the SP value can be estimated only from the chemical structure according to the Fedors method (see "Solubility Parameter Values", Polymer Handbook, 4th edition (edited by J, Brandrup et al.)) . In this specification, the SP value means a value calculated by the Fedors method, and the lower the value, the lower 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, but is usually 17.0 (J / cm ³ ) ^0.5 or more.

If it is a photopolymerizable monomer exhibiting such SP value (B), while maintaining good compatibility with the (meth) acrylate oligomer (A), the polarity of the monomer itself has decreases effectively. And since the photopolymerizable monomer (B) used has low polarity, it can greatly contribute to the improvement of the compatibility of the fluorine compound and / or silicon compound (C) described later , and the photopolymerizable composition obtained therefrom When the coating layer is formed by curing, it is estimated that the reactivity of the cured coating layer itself can be sufficiently suppressed. As described above, the functional panel of the present invention in which the coating layer is formed has excellent antifouling property because the fluorine compound and / or silicon compound (C) exhibits very good compatibility. It does not react more than necessary with a cleaning agent, a dyeing agent, etc., can maintain good hot water resistance, and can also exhibit good chemical resistance and dyeing resistance.

The photopolymerizable monomer (B) is preferably a (meth) acrylate monomer having at least one acryloyloxy group (CH ₂ ═CHCOO—) or methacryloyloxy group (CH ₂ ═C (CH ₃ ) COO—). Any of a monofunctional monomer, a bifunctional monomer, and a polyfunctional monomer may be used.

Examples of the monofunctional monomer include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) ) Alicyclic (meth) acrylates such as acrylate; benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate , methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate , Butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, Sil (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, isostearyl (meth) acrylate.

Examples of the bifunctional monomer include ethylene glycol di (meth) acrylate , 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth). ) Acrylate, neopentyl glycol di (meth) acrylate , tricyclodecane dimethanol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, and the like .

Examples of the polyfunctional monomer, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate. These photopolymerizable monomers may be used alone or in combination of two or more.

In addition, SP value at the time of using 2 or more types of photopolymerizable monomers (B) is the SP value of each monomer in the SP value of each monomer. It means the value obtained by multiplying by the monomer ratio) and adding them. For example, when the photopolymerizable monomer (B) has a total amount of 1 and a photopolymerizable monomer having an SP value of 19.0 is blended in 3/4 and a photopolymerizable monomer having an SP value of 21.0 in an amount of 1/4, The SP value of the entire photopolymerizable monomer (B) used is determined according to the following formula (X).
SP value of photopolymerizable monomer (B) = (19.0 × 3/4) + (21.0 × 1/4) = 19.5 (X)

The photopolymerizable monomer (B) is a monomer represented by the following formula (1) .
(CH ₂ = CR ¹ COO) _n R ² (1)

In said formula (1), R < ¹ > shows 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, does not include a hetero atom, and may be a chain or a ring. Further, —CH ₂ — in the group may be replaced with —CH═CH—. n shows the integer of 1-4.

That is, in the above formula (1), for example if it is a saturated monomer a chain, R ² when n = 1 becomes a alkyl group having 5 to 20 carbon atoms, R ² when n = 2 the carbon It becomes an alkylene group of formula 5-20. Further, when it is a chain and a saturated monomer, R ² becomes an alkanetriyl group having 5 to 20 carbon atoms when n = 3, and an alkanetetrayl group having 5 to 20 carbon atoms when n = 4. It becomes. Examples of such R ² include —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) CH ₃ , a cyclohexyl group, a cycloheptane group, a cyclooctane group, a cyclononane group, a cyclodecane group, and the like. An alkyl group, an alkylene group such as —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ —, an alkanetriyl group represented by the following formula (2), There is an alkanetetrayl group represented by the following formula (3).

When the carbon number of R ² is less than 5, the SP value of the monomer tends to increase in the case of a chain hydrocarbon group, and the acquisition itself becomes difficult in the case of a cyclic hydrocarbon group. Moreover, when the carbon number of R ² exceeds 20, in the case of a cyclic hydrocarbon group, the crosslinking density of the resulting photopolymerizable composition tends to decrease. If the crosslink density is lowered more than necessary, a staining agent such as a hair color is likely to be leached into the coating layer, and the panel may be dyed.

  Specific examples of the monomer represented by the above formula (1) include isobornyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, and isoamyl (meta). ) Acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 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. Of these, 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isobornyl (meth) acrylate, and dimethyloltricyclodecane di (meth) acrylate are preferable, and 1,9- Nonanediol di (meth) acrylate and dimethyloltricyclodecane di (meth) acrylate are more preferable. Such a monomer tends to exhibit good low polarity because it has a more suitable SP value, and not only the antifouling property of the resulting functional panel, but also chemical resistance and dye resistance. It becomes possible to improve. Moreover, the function as a reactive diluent of the said low polar (meth) acrylate oligomer (A) can also be exhibited effectively.

Further, functional groups of the photo-polymerizable monomer (B) is 1-4. When the number of functional groups is 1, the crosslinking density tends to increase. However, when the number of functional groups is 2 to 4, the crosslinking reaction of the photopolymerizable composition tends to be appropriately maintained. In particular, it is presumed that the phenomenon in which the stain is leached into the coating layer and the panel is dyed can be more effectively suppressed. Therefore, in this case as well, a functional panel in which a coating layer having suitable curability is formed while effectively retaining not only good antifouling properties but also chemical resistance and dyeing resistance can be obtained. .

[ Fluorine compound and / or silicon compound (C)]
The photopolymerizable composition of the present invention contains a fluorine compound and / or a silicon compound (C). Fluorine compounds and / or silicon compound, by surface free energy rather small, to reduce the wettability of the photopolymerizable composition by containing it, to form a coating layer made of such a composition on a substrate By increasing the water contact angle, it is possible to suppress the adhesion of various stains typified by scale and improve the antifouling property of the functional panel.

A fluorine compound and / or a silicon compound (C) may be used individually by 1 type, and may be used in combination of 2 or more type. Specifically, the fluorine compound is a compound having at least one skeleton selected from the group consisting of —CF ₃ , —CF ₂ H, —CF ₂ CF ₂ —, and —CF ₂ CFH—. Is desirable. These skeletons are more suitable ascending. As a commercially available fluorine compound, Modiper F200 (manufactured by NOF Corporation), OPTOOL DAC (manufactured by Daikin Industries, Ltd.) and the like can be used.

上記式（ii）中、ｑは１〜２００の整数を示す。かかるケイ素化合物としては、サイラプレーン（チッソ製）、ジメチルシリコーンオイル（信越シリコーン製）等の上市のシリコーンオイルを用いることができる。 Specifically, the silicon compound is preferably a compound having a dimethylsiloxane skeleton represented by the following formula (ii).

In said formula (ii), q shows the integer of 1-200. As the silicon compound, commercially available silicone oils such as Silaplane (manufactured by Chisso) and dimethyl silicone oil (manufactured by Shin-Etsu Silicone) can be used.

[Photopolymerizable composition]
Functional photopolymerizable composition used in the panel of the present invention, contain a (meth) acrylate oligomer (A), a photopolymerizable monomer (B), the fluorine compound and / or a silicon compound (C) Yes. The blending amount of the ( meth) acrylate oligomer (A) and the photopolymerizable monomer (B) is usually 80:20 to 20:80, preferably 30:70 to 70:30, in mass ratio. If the blending amount of the monomer is too small, the viscosity of the resulting photopolymerizable composition may increase and applicability may deteriorate, and physical properties such as chemical resistance and dye resistance may not be sufficiently secured. is there. Moreover, when there are too many compounding quantities of a monomer, it exists in the tendency for the softness | flexibility of a coating film to fall and for brittleness to become high. Therefore , when the blending amount of the (meth) acrylate oligomer (A) and the photopolymerizable monomer (B) is within the above range, the low polarity of the photopolymerizable monomer (B) can be sufficiently exhibited. Also, due to these SP values, the chemical panel and the dyeing resistance of the functional panel are improved , and the excellent compatibility of the fluorine compound and / or silicon compound (C) is ensured to provide good antifouling properties. It becomes possible to demonstrate. Further, it becomes possible to photopolymerizable monomer (B) acts as an effective diluent with respect to (meth) acrylate oligomer (A), a photopolymerizable composition is easily exhibited appropriate viscosity, good coating properties Can also be provided.

Moreover, the compounding quantity of a fluorine compound and / or a silicon compound (C) is 0.1-5. Normally with respect to a total of 100 mass parts of the said (meth) acrylate oligomer (A) and a photopolymerizable monomer (B). The amount is 0 parts by mass, preferably 0.1 to 4.0 parts by mass, more preferably 0.1 to 3.0 parts by mass. If the blending amount of the fluorine compound and / or silicon compound (C) is less than 0.1 parts by mass, sufficient antifouling property may not be realized. If it exceeds 5.0 parts by mass, the coating film is more than necessary. There is a possibility that the hard coat property may be impaired due to softening, and the amount of the compound for which compatibility cannot be sufficiently secured may be increased.

  The photopolymerizable composition includes, in addition to the photopolymerizable monomer (B) having the predetermined SP value as a monomer, in addition to the photopolymerizable monomer (B), as long as the effects of the present invention are not impaired. The monomer may be contained. That is, when blending other monomers, the SP value calculated from the SP value of each of the other monomers according to the above formula (X) may be within the range of the SP value.

  A known photopolymerization initiator can be used for the photopolymerizable composition. The photopolymerization initiator has an effect of initiating polymerization of the above-described low-polarity (meth) acrylate oligomer (A) and photopolymerizable monomer (B) by irradiating with ultraviolet rays. Specific examples of the photopolymerization initiator include 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, 2,2-dimethoxy-2-phenylacetophenone, acetophenone diethyl ketal, alkoxyacetophenone, and benzyldimethyl. Ketal, benzophenone and benzophenone derivatives such as 3,3-dimethyl-4-methoxybenzophenone, 4,4-dimethoxybenzophenone, 4,4-diaminobenzophenone, alkyl benzoylbenzoate, bis (4-dialkylaminophenyl) ketone, benzyl and Benzyl derivatives such as benzyl methyl ketal, benzoin derivatives such as benzoin and benzoin isobutyl ether, benzoin isopropyl ether, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl Nilketone, xanthone, thioxanthone and thioxanthone derivatives, fluorene, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,2-benzyl-2-dimethylamino-1- (morpholinophenyl) -butanone- 1 etc. are mentioned. These photopolymerization initiators may be used alone or in combination of two or more. The compounding quantity of the photoinitiator in the said photopolymerizable composition is 0.1-10 with respect to a total of 100 mass parts of the said low polar (meth) acrylate oligomer (A) and a photopolymerizable monomer (B). An amount in the range of parts by mass is desirable. When the amount of the photopolymerization initiator is less than 0.1 parts 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, while the cost of the raw material is high. Become.

  In addition, the photopolymerizable composition may further contain a photosensitizer as necessary in consideration of required curing reactivity and stability. The photosensitizer absorbs energy when irradiated with light, and the energy or electrons move to the polymerization initiator to initiate polymerization. Examples of the photosensitizer include p-dimethylaminobenzoic acid isoamyl ester. The compounding quantity of these photosensitizers is the quantity of the range of 0.1-10 mass parts with respect to a total of 100 mass parts of the said low polar (meth) acrylate oligomer (A) and a photopolymerizable monomer (B). It is desirable that

  Furthermore, in consideration of the required curing reactivity and stability, the photopolymerizable composition may contain a polymerization inhibitor as necessary. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-p-cresol, butylhydroxyanisole, Examples include 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, 2,5-dihydroxy-p-quinone, and the like. These polymerization inhibitors are blended in an amount in the range of 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the low polarity (meth) acrylate oligomer (A) and the photopolymerizable monomer (B). It is desirable.

  In addition, the photopolymerizable composition used for forming the coating layer may contain an organic solvent such as ether, ketone or ester as a diluting solvent. As the organic solvent, propylene glycol monomethyl ether acetate (PMA) is used. , 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 applied to the surface of the substrate as a coating liquid using a diluting solvent as necessary. A known method can be adopted as a coating method, such as gravure coating, roll coating, reverse coating, knife coating, die coating, lip coating, doctor coating, extrusion coating, slide coating, wire bar coating, curtain coating, extrusion. Examples thereof include a coat and a spin coat.

[Coating layer]
The said photopolymerizable composition is apply | coated on a base material, Then, an application layer is formed on a base material layer by carrying out photocuring. As a photocuring method, a method of irradiating with ultraviolet rays is generally used. The surface on the base material layer forming the coating layer may be only one surface or both surfaces of the front surface and the back surface, and may be appropriately selected as necessary. The irradiation amount of light for curing the photopolymerizable composition, when employing ultraviolet light, usually, irradiation intensity 20~2000mW / cm ^2, an irradiation amount 100~5000mJ / cm ^2, whereby the light The polymerizable composition is usually cured in several seconds to several tens of seconds. Thus, since it can be hardened in a short time, productivity improvement of the functional panel obtained can be aimed at.

  The thickness of the coating layer can be appropriately selected from the required degree of design and chemical resistance, and is not particularly limited, but is normally assumed to be in the range of 1 μm to 200 μm.

In addition, when irradiating with ultraviolet rays, since the ultraviolet curing reaction is a radical reaction, it is susceptible to inhibition by oxygen. Therefore, after applying the photopolymerizable composition to a substrate, the composition may be cured under a nitrogen atmosphere so that contact with oxygen can be avoided.
In addition, the surface free energy of the coating layer formed by photocuring is usually preferably 12 to 30 mJ / m ² from the viewpoint of sufficiently ensuring good antifouling properties.

[Base material layer]
The material of the base material layer used for the functional panel of the present invention includes inorganic materials such as slate, concrete, metal, calcium silicate, calcium carbonate, glass; wood material, polypropylene, polystyrene, polycarbonate, unsaturated polyester resin Organic materials such as these; and composite materials thereof. Among them, a material obtained by adding fibers such as glass fiber and carbon fiber to an organic material, that is, so-called FRP (fiber reinforced plastic) is preferable. Examples of the FRP include an unsaturated polyester resin, a sheet-like sheet molding compound (SMC) containing glass fiber or carbon fiber, a bulky BMC which is a composite material similar to SMC and contains short fibers. In general, FRP is a blend of a thermosetting resin, an organic peroxide (curing agent), a filler, a low shrinkage agent, an internal mold release agent, a reinforcing material, a crosslinking agent, a thickener, and the like. It is used by being put in a mold set at a predetermined temperature and pressurized, and shaped into a shape according to the place to be arranged as a building material. In particular, when the FRP contains unsaturated polyester as a thermoplastic resin, a filler, and glass fiber or carbon fiber as a reinforcing material, the strength and durability of the entire functional panel obtained can be further improved.

  Unsaturated polyesters include polybasic unsaturated acids such as maleic anhydride and fumaric acid, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, trimethylpentanediol, neopentyl glycol, trimethylpropane monoallyl. It is produced from polyhydric alcohols such as ether, hydrogenated bisphenol and bisphenol dioxypropyl ether.

  Examples of the filler include calcium carbonate and aluminum hydroxide. Calcium carbonate is preferable from the viewpoint of cost reduction, and aluminum hydroxide is preferable from the viewpoint of improving the chemical resistance of FRP itself. However, as described above, if the coating layer is formed, the chemical resistance of the entire functional panel can be sufficiently improved even if FRP using calcium carbonate as a filler is used as the base material. A functional panel having a base material layer made of cost FRP can be easily realized.

  Glass fibers and carbon fibers as reinforcing materials having a fiber length of about 20 to 50 mm and a fiber diameter of about 5 to 25 μm are preferably used, and are contained in FRP in an amount of 10 to 70% by mass. Is desirable. The FRP used as the base material layer is manufactured as an FRP having a predetermined thickness and size by mixing these components and using an FRP manufacturing apparatus or the like.

  In addition, although the thickness of a base material layer may be fluctuate | varied with the use of a functional panel, it is 2.5 mm or more normally. The upper limit of the thickness is not particularly limited and can be appropriately selected.

[Function panel]
The functional panel of the present invention includes the coating layer and the base material layer, and the coating layer is formed on the base material layer. The thickness of the entire functional panel is usually preferably 2.5 mm or more. The upper limit of the thickness of the entire functional panel is not particularly limited, and the coating layer may be formed on both the front surface and the back surface of the base material layer, and if necessary, in addition to the base material layer and the coating layer, A multilayer structure in which an intermediate layer made of various materials is formed between these layers may be used. At this time, since the coating layer exhibits not only excellent antifouling properties as described above, but also chemical resistance and dyeing resistance, it is desirable to form the coating layer as the outermost surface layer of the functional panel. As an intermediate | middle layer, the undercoat layer for improving the adhesiveness of a base material layer and a coating layer, the decorative layer which provided the pattern and color for improving the designability of a functional panel, etc. are mentioned, for example.

  The functional panel of the present invention thus obtained has excellent antifouling properties as well as warm water resistance, chemical resistance, and dye resistance because the specific coating layer is formed on the base material layer. In addition, it effectively suppresses the adhesion of various types of dirt, such as scale, and is unlikely to be altered or deteriorated by the use of a highly irritating detergent containing acid or alkali. In addition, discoloration and dyeing hardly occur even when a dyeing agent such as a hair color is used. Therefore, the functional panel of the present invention is particularly suitable as a functional panel disposed in a bathroom or kitchen in a house.

  In addition, if FRP containing unsaturated polyester resin and glass fiber or carbon fiber is adopted as the base material layer, not only excellent antifouling property, chemical resistance and dyeing resistance, but also excellent durability is imparted. Functional panels can be realized.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

[Production Example 1: Preparation of oligomer (a)]
A polyol was obtained by adding 6 mol of ethylene oxide to 1 mol of glycerin (manufactured by Kanto Chemical Co., Ltd.) using potassium hydroxide as a catalyst at a reaction temperature of 110 ° C. To the above polyol, 3 mol of 2,4-tolylene diisocyanate was charged into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer and a cooling tube, and reacted at 70 ° C. for 2 hours.

  Next, 6 mol of 2-hydroxyethyl acrylate and a small amount of dibutyltin dilaurate as a catalyst are gradually added, and further reacted at 70 ° C. for 15 hours to obtain a urethane acrylate oligomer (a) having a polyethylene oxide unit having a weight average molecular weight of about 1300. Obtained.

[Production Example 2: Preparation of oligomer (b)]
A polyol was obtained by adding 6 mol of propylene oxide to 1 mol of glycerin (manufactured by Kanto Chemical Co., Inc.) using potassium hydroxide as a catalyst at a reaction temperature of 110 ° C. To the above polyol, 3 mol of 2,4-tolylene diisocyanate was charged into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer and a cooling tube, and reacted at 70 ° C. for 2 hours.

  Next, 6 mol of 2-hydroxyethyl acrylate and a small amount of dibutyltin dilaurate as a catalyst are gradually added, and further reacted at 70 ° C. for 15 hours to obtain a urethane acrylate oligomer (b) having a polypropylene oxide unit having a weight average molecular weight of about 1300. Obtained.

[Production Example 3: Preparation of oligomer (c)]
To 1 mol of CaPa3050 (manufactured by Perstorp), 3 mol of 2,4-tolylene diisocyanate was charged into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer and a cooling tube, and reacted at 70 ° C. for 2 hours.

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

[Production Example 4: Preparation of oligomer (d)]
Polyol was obtained by adding 12 mol of butylene oxide to 1 mol of propylene glycol (manufactured by Kanto Chemical Co., Inc.) using potassium hydroxide as a catalyst at a reaction temperature of 110 ° C. To the above polyol, 2 mol of 2,4-tolylene diisocyanate was charged into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer and a cooling tube, and reacted at 70 ° C. for 2 hours.

  Next, 4 mol of 2-hydroxyethyl acrylate and a small amount of dibutyltin dilaurate as a catalyst are gradually added, and further reacted at 70 ° C. for 15 hours to obtain a urethane acrylate oligomer (x) having a weight average molecular weight of about 1500 butylene oxide units (x). Obtained.

  A polyol was obtained by adding 4 mol of butylene oxide to 1 mol of pentaerythritol (manufactured by Kanto Chemical Co., Inc.) using potassium hydroxide as a catalyst at a reaction temperature of 110 ° C. To the polyol, 4 mol of 2,4-tolylene diisocyanate was charged into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer and a cooling tube, and reacted at 70 ° C. for 2 hours.

  Next, 8 mol of 2-hydroxyethyl acrylate and a slight amount of dibutyltin dilaurate as a catalyst are gradually added, and further reacted at 70 ° C. for 15 hours to obtain a urethane acrylate oligomer (y) having a weight average molecular weight of about 1500 butylene oxide units (y). Obtained.

  The urethane acrylate oligomer (x) and the urethane acrylate oligomer (y) are mixed so as to have an acrylic functional group ratio of 50:50, and 1,2-polybutylene oxide unit having an average functional group number of 3 and a weight average molecular weight of about 1500. A urethane (meth) acrylate oligomer (d) having

[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., Inc.) using potassium hydroxide as a catalyst at a reaction temperature of 110 ° C. To the above polyol, 2 mol of 2,4-tolylene diisocyanate was charged into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer and a cooling tube, and reacted at 70 ° C. for 2 hours.

  Next, 4 mol of pentaerythritol triacrylate and a small amount of dibutyltin dilaurate as a catalyst are gradually added, and further reacted at 70 ° C. for 15 hours, whereby a urethane acrylate oligomer having a 1,2-polybutylene oxide unit having a weight average molecular weight of about 1600 is obtained. (E) was obtained.

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

<< Measurement of n-heptane tolerance >>
While maintaining 10 g of various oligomers at 25 ° C., n-heptane was added dropwise thereto until it became cloudy, and the amount (g) of n-heptane at this time was measured (unit: g / 10 g).

[Examples 1-3, Comparative Examples 1-5]
In accordance with the blending amounts shown in Tables 2 to 3, various oligomers and photopolymerizable monomers were added to a stirrer and mixed, and further a low surface free energy compound was added, followed by a photopolymerization initiator (IRGACURE 184, Ciba Specialty). 1 part by mass of Chemicals Co., Ltd. was added and stirred for 2 minutes, followed by defoaming treatment to obtain each photopolymerizable composition.

Using the obtained photopolymerizable composition, the compatibility of the fluorine compound and / or silicon compound (C) in the composition was evaluated according to the following method. The results are shown in Tables 2-3.

<< Evaluation of compatibility >>
The obtained photopolymerizable composition was visually evaluated and evaluated as good when it exhibited good compatibility and was transparent, and when it was clearly cloudy or separated into layers.

* 1: Fluorine compound, Modiper F200 (manufactured by NOF Corporation)
* 2: Silicon compound, TSF4452, manufactured by Momentive Performance Materials Japan * 3: Fluorine compound, Optool DAC (manufactured by Daikin Industries, Ltd.)
* 4: Silicon compound, Silaplane FM7725 (manufactured by Chisso)
* 5: Blending amount of oligomer and monomer with respect to 100 parts by mass in total * 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: Acryloylmorpholine (manufactured by Shin-Nakamura Chemical 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 said result, Examples 1-3 which mix | blended (meth) acrylate oligomer (A) and the photopolymerizable monomer (B) are excellent also when mix | blending any fluorine compound or silicon compound (C). It can be seen that even when the blending amount is reduced, the characteristics are maintained.

Claims (6)

(A) The following formula (i):

Wherein (i), m represents an integer of 1 to 200] have a 1,2-polybutylene oxide unit represented by is n- heptane tolerance 0.5 g / 10 g or more (meth) acrylate An oligomer,
(B) solubility parameter (SP value) Ri der 20.0 (J / cm ^{3) 0.5} or less, the following equation (1):
(CH ₂ = CR ¹ COO) _n R ² (1)
[In 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, n is an integer of 1-4] you express in A photopolymerizable monomer;
(C) a fluorine compound and / or a silicon compound ,
0.1 to 5.0 parts by mass of the fluorine compound and / or silicon compound (C) with respect to a total of 100 parts by mass of the (meth) acrylate oligomer (A) and the photopolymerizable monomer (B). A photopolymerizable composition comprising: The (meth) acrylate oligomer (A) is a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, an ether (meth) acrylate oligomer, an ester (meth) acrylate oligomer, or a polycarbonate (meth) acrylate oligomer. The photopolymerizable composition according to claim 1, wherein the photopolymerizable composition is a fluorine-based (meth) acrylate oligomer or a silicone-based (meth) acrylate oligomer . The photopolymerizable composition according to claim 1, wherein the (meth) acrylate oligomer (A) has a weight average molecular weight of 400 to 100,000 by GPC . The fluorine compound is a compound having at least one skeleton selected from the group consisting of —CF ₃ , —CF ₂ H, —CF ₂ CF ₂ —, and —CF ₂ CFH—;
The silicon compound is represented by the following formula (ii):

The photopolymerizable composition according to any one of claims 1 to 3, wherein the photopolymerizable composition is a compound having a dimethylsiloxane skeleton represented by [in the formula (ii), q represents an integer of 1 to 200] . . Amount of the (meth) acrylate oligomer (A) and the photopolymerizable monomer (B) is, in mass ratio, 80: 20 to 20: the claims 1-4, characterized in that the amount of 80 The photopolymerizable composition in any one.   A functional panel comprising a coating layer formed by curing the photopolymerizable composition according to claim 1 and a base material layer.