JP2014139010A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in weather resistance and capable of achieving both of crack prevention effect and contamination suppression effect.SOLUTION: The laminate has an intermediate coat layer and a finish coat layer on a surface of a plasticizer-containing material, the intermediate coat layer is a layer formed of an intermediate coating material containing (A) a polyol compound, (B) a polyisocyanate compound having the content of an isocyanate group of 5 wt.% to 20 wt.%, and (C) a tetraalkoxysilane compound, and the finishing coat later is a layer formed of a finish coating material (D) containing a fluorine resin.

Description

  The present invention relates to a novel laminate, and can be applied mainly to the field of construction and civil engineering.

  Conventionally, for buildings, civil engineering structures, etc., surface finishing with various laminates using sheets, coating films, films, panels, tiles, etc. has been performed to protect the frame, impart design and improve aesthetics. It has been broken. For example, a laminated body using a waterproof material such as a coating film waterproof material or a sheet waterproof material is widely used for a portion that is required to be waterproof, such as an outer wall, a roof, a rooftop, a veranda, a balcony, and a floor. Moreover, in the joint part of various building materials, the sealing material is used in order to provide waterproofness etc.

  However, such waterproofing materials and sealing materials are often insufficient in weather resistance, and the waterproof performance may deteriorate due to various deterioration factors including ultraviolet rays of sunlight. is there. Therefore, in order to protect the material from these deterioration factors and improve the weather resistance, an overcoat layer of an overcoat material is often laminated.

  As the overcoat layer, a urethane resin is generally used because of physical properties such as weather resistance and flexibility of the film. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2005-299103) shows that a two-component acrylic urethane coating material is used as a topcoat (top coating material) layer of a waterproof coating layer. Patent Document 2 (Japanese Patent Application Laid-Open No. 2006-104673) shows that a two-pack type acrylic urethane resin composition is used as a top coat layer of a waterproof sheet.

  However, in recent years, the demand for weather resistance is increasing, and higher weather resistance beyond the level of general urethane resin may be required. In that case, for example, a top coating material using a resin having higher weather resistance such as a fluororesin is required. Since fluororesin has performance superior to urethane resin in terms of weather resistance, durability, chemical resistance, etc., if fluororesin is used as the top coating material, the maintenance cycle can be greatly extended, and the life cycle It is known that costs can be reduced.

  An example in which a fluororesin is used as an overcoat material includes Patent Document 3 (Japanese Patent Laid-Open No. 2004-263121). Patent Document 3 discloses a two-pack type topcoat composition for waterproofing material containing a fluoroolefin copolymer having a fluorine content of 5% or more, a polyisocyanate curing agent having flexibility, and the like. According to the composition of this document, it can be expected that superior weather resistance can be imparted as compared with the urethane resin-based topcoat composition.

JP-A-2005-299103 JP 2006-104673 A JP 2004-263121 A

  However, waterproofing materials and sealing materials generally contain a plasticizer in order to impart flexibility and suppress cracking, and this plasticizer may migrate to the surface of the overcoat layer over time. There is. When the topcoat layer is a fluororesin, such problems are likely to occur, and even if the weather resistance is increased, contaminants in the air may adhere to the surface of the topcoat layer and the aesthetics may deteriorate. .

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a laminate that is excellent in weather resistance and can achieve both a crack prevention effect and a contamination suppression effect.

  In order to solve the above problems, the present inventor, as a result of intensive studies, laminated a fluororesin-based overcoat layer on the surface of the plasticizer-containing material via an intermediate coating layer formed of a specific intermediate coating material. As a result, the present invention has been completed.

That is, the present invention has the following characteristics.
1. A laminate having an intermediate coating layer and a top coating layer on the surface of the plasticizer-containing material,
The intermediate coating layer is formed of an intermediate coating material containing (A) a polyol compound, (B) a polyisocyanate compound having an isocyanate group content of 5% by weight to 20% by weight, and (C) a tetraalkoxysilane compound. Layer,
The laminate is characterized in that the overcoat layer is a layer formed of (D) a topcoat material containing a fluororesin.
2. The component (A) contains (A-1) a polyol compound having an amino group and / or a carboxyl group. The laminated body as described in.
3. The component (A) contains (A-2) polycaprolactone diol and / or polycaprolactone triol. Or 2. The laminated body as described in.
4). The top coat layer is formed of a top coat material containing (D) a fluororesin and (E) a tetraalkoxysilane compound. ~ 3. The laminated body in any one of.

  In the laminate of the present invention, a fluororesin-based overcoat layer is laminated on the surface of a plasticizer-containing material via an intermediate coat layer formed of a specific intermediate coat material, so that the plasticizer to the topcoat layer can be obtained. This suppresses migration, exhibits excellent weather resistance, and enables both cracking prevention effects and contamination prevention effects.

  Hereinafter, modes for carrying out the present invention will be described.

  The laminate of the present invention has a specific intermediate coating layer and top coating layer on the surface of the plasticizer-containing material. Among these, the plasticizer-containing material is a material containing a resin and a plasticizer as essential components. Specific examples of the plasticizer-containing material include a waterproof material such as a waterproof coating material and a waterproof sheet material, and a sealing material. The present invention is particularly applicable to waterproof materials such as a waterproof coating material and a waterproof sheet material.

  The waterproof coating material is a composition containing a highly elastic resin as a main component and a filler or the like as necessary. A roller, a brush, a spray gun or the like is used so that the thickness is about 1 to 5 mm. It is applied and formed into a film and cured to form a seamless layer having elasticity and waterproofness. Examples of the waterproof coating material include urethane rubber, acrylic rubber, chloroprene rubber, rubber asphalt, silicone rubber, and polymer cement.

  The waterproof sheet is made by cutting a sheet with a thickness of approximately 1mm to 2mm, which is mainly composed of petroleum-derived materials such as vinyl chloride resin, into a required area, and fixing it to the base with an adhesive or metal tool. It sticks them together. Examples of the waterproof sheet include a vinyl chloride sheet and a polyethylene sheet.

  The sealing material is applied to a joint portion or the like of the base material, and ensures joining and waterproofing of the joint portion. Examples of the sealing material include silicone-based sealing materials, modified silicone-based sealing materials, polysulfide-based sealing materials, modified polysulfide-based sealing materials, acrylic urethane-based sealing materials, polyurethane-based sealing materials, SBR-based sealing materials, and butyl rubber-based sealing materials. Can be mentioned. These may be either a one-component form or a two-component form.

  Examples of plasticizers contained in such materials include phthalates such as dioctyl phthalate, dibutyl phthalate, and butyl benzyl phthalate, dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate. Examples include aliphatic carboxylic acid esters, alcohol esters such as pentaerythritol ester, phosphoric acid esters such as trioctyl phosphate and tricresyl phosphate, and chlorinated paraffin. The plasticizer content in the plasticizer-containing material is preferably 0.1% by weight or more and 50% by weight or less.

  The intermediate coating layer in the present invention is formed by an intermediate coating material containing (A) a polyol compound, (B) a polyisocyanate compound having an isocyanate content of 5% by weight to 20% by weight, and (C) a tetraalkoxysilane compound. Is done.

  Examples of (A) polyol compounds (hereinafter also referred to as “component (A)”) include polyether polyols, polyester polyols, acrylic polyols, and the like, and in addition, phenol resin polyols, epoxy polyols, polybutadiene polyols, polyisoprene polyols. It is also possible to use polyester-polyether polyol, urea-dispersed polyol, carbonate polyol, and the like. As the component (A), one or more of these can be used, and among these, it is desirable to include an acrylic polyol.

  Examples of the polyether polyol include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, glucose, sorbitol, sucrose, propylene oxide, ethylene oxide, butylene oxide. And polyols obtained by adding styrene oxide or the like.

  Examples of the polyester polyol include polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, pentaerythritol, glutaric acid, adipic acid, pimelic acid, Examples thereof include condensation polymers with polyvalent carboxylic acids such as speric acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, and hydrogenated dimer acid.

  As the acrylic polyol, those obtained by polymerizing a hydroxyl group-containing acrylic monomer and, if necessary, other monomers can be used. Among these, as the hydroxyl group-containing acrylic monomer, for example, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid- Examples thereof include hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxybutyl and (meth) acrylic acid-4-hydroxybutyl, and one or more of these can be used.

  Examples of other monomers constituting the acrylic polyol include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and n-amyl. (Meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate (Meth) acrylic acid alkyl esters such as cyclohexyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylamino (meth) acrylate Amino group-containing monomers such as relate, aminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate; acrylic acid, methacrylic acid, crotonic acid, maleic acid or monoalkyl ester thereof, itaconic acid or monoalkyl ester thereof, fumaric acid or Carboxyl group-containing monomers such as monoalkyl esters; Amide-containing monomers such as (meth) acrylamide and ethyl (meth) acrylamide; Nitrile group-containing monomers such as (meth) acrylonitrile; Epoxy group-containing monomers such as glycidyl (meth) acrylate; Aromatic hydrocarbon monomers such as styrene, methylstyrene, chlorostyrene, vinyltoluene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, etc. One or more of these can be used if necessary.

  The hydroxyl value of the component (A) is preferably 10 KOH mg / g or more and 200 KOH mg / g or less, more preferably 20 KOH mg / g or more and 100 KOH mg / g or less. The hydroxyl value is a value represented by the number of mg of potassium hydroxide equimolar to the hydroxyl group contained in 1 g of the sample. JIS K 1557-1: 2007 Plastic-polyurethane raw material polyol test method-Part 1: hydroxyl group It is a value measured based on how to obtain the value. The hydroxyl value of (A) component is the value measured with the mixture of all the (A) components.

In the present invention, as the component (A), it is preferable to contain (A-1) a polyol compound having an amino group and / or a carboxyl group (hereinafter also referred to as “(A-1) component”). The effect of this invention can be improved further by containing 1 or more types of such (A-1) component.
Examples of (A-1) include a polyol having an amino group, a polyol having a carboxyl group, a polyol having an amino group and a carboxyl group, and one or more of these can be used. For example, an embodiment including a polyol compound having an amino group and a polyol compound having a carboxyl group as the component (A-1) is also suitable.

  As (A-1) component, what copolymerized the amino group containing monomer and / or the carboxyl group containing monomer can be used, for example. As the component (A-1) in the present invention, an acrylic polyol having an amino group and / or a carboxyl group is particularly suitable. As such an acrylic polyol, among the above-mentioned other monomers, those using an amino group-containing monomer and / or a carboxyl group-containing monomer, that is, at least a hydroxyl group-containing acrylic monomer, and an amino group-containing monomer and / or a carboxyl group-containing What copolymerized the monomer can be used.

  The ratio of the amino group-containing monomer in the component (A-1) is preferably 0.1% by weight or more and 40% by weight or less, more preferably 0.5% by weight or more and 30% by weight in the constituent components of the component (A-1). % Or less.

  As the carboxyl group-containing monomer in the component (A-1), (meth) acrylic acid is particularly suitable. The ratio of the carboxyl group-containing monomer is preferably 0.1% by weight or more and 40% by weight or less, more preferably 0.5% by weight or more and 20% by weight or less in the constituent components of the component (A-1).

  Moreover, in this invention, it is preferable to contain (A-2) polycaprolactone diol and / or polycaprolactone triol (henceforth "(A-2) component") as (A) component. By containing such a component (A-2), the effect of preventing cracks can be further enhanced.

  The content of the component (A-2) is preferably 1% by weight or more and 20% by weight or less, more preferably 2% by weight or more and 15% by weight or less in the component (A) in terms of solid content. If it is such a range, it is preferable from surfaces, such as a softness | flexibility of a film, and an external appearance.

The amine value of the component (A) is preferably 0.01 KOH mg / g or more and 20 KOH mg / g or less, more preferably 0.1 KOH mg / g or more and 10 KOH mg / g or less.
The amine value is the amount of the base identified as amine expressed in milligrams (mg) of potassium hydroxide in 1 g of a sample obtained by titration with perchloric acid, and JIS K 1557-7: 2011 Plastic-polyurethane raw material Polyol test method-Part 7: Values measured based on how to determine basicity (nitrogen content and total amine value display). The amine value of (A) component is the value measured with the mixture of all the (A) components.

  The acid value of the component (A) is preferably from 0.1 KOH mg / g to 10 KOH mg / g, more preferably from 1 KOH mg / g to 8 KOH mg / g. The acid value is the number of mg of potassium hydroxide required to neutralize the acid component present in 1 g of the sample. JIS K 5601-2-1: 1999 Paint component test method “acid value (titration method) Is a value measured based on The acid value of (A) component is the value measured with the mixture of all the (A) components.

  (B) The polyisocyanate compound (hereinafter also referred to as “component (B)”) has two or more isocyanate groups in one molecule and reacts with the component (A) to form an intermediate coating layer. It becomes a component. As (B) component, what can be bridge | crosslinked with (A) component at normal temperature is suitable. In addition, normal temperature here refers to about −10 ° C. to 50 ° C., preferably 5 ° C. to 40 ° C.

  Examples of the component (B) include toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (pure-MDI), polymeric MDI, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), and water. Derivatives derived from isocyanate monomers such as added XDI and hydrogenated MDI by alphatonation, biuretization, dimerization (uretidioneization), trimerization (isocyanurate), adduct formation, carbodiimidization reaction, and mixtures thereof Is mentioned. These can be used alone or in combination of two or more.

  In the present invention, the component (B) having an isocyanate group content of 5% by weight to 20% by weight is used. By using such a component (B), it is possible to obtain the effect of suppressing contamination due to migration of the plasticizer, together with excellent weather resistance and crack followability. When the isocyanate group content is less than 5% by weight, the effects of the present invention cannot be sufficiently obtained. On the other hand, when the isocyanate group content is larger than 20% by weight, the coating becomes too hard, so that it is difficult to follow the plasticizer-containing material, and there is a risk of cracking.

  In the present invention, the isocyanate group content is defined as the content (% by weight) of the isocyanate group contained in the solid content of the polyisocyanate compound. After neutralizing the isocyanate group with an excess of amine, It is a value obtained by back titration.

  What is necessary is just to set the mixing ratio of (B) component in consideration of the NCO / OH ratio with respect to the hydroxyl group of (A) component. The NCO / OH ratio between the hydroxyl group of component (A) and the isocyanate group of component (B) is preferably from 0.6 to 1.4, more preferably from 0.8 to 1.2. With such a ratio, the effect of the present invention can be further enhanced.

  The (C) tetraalkoxysilane compound (hereinafter also referred to as “component (C)”) in the intermediate coating layer contributes to prevention of plasticizer migration. As the component (C), tetraalkoxysilane, condensate of tetraalkoxysilane, and modified products thereof can be used. Examples of tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetra-t-butoxysilane, tetra Examples include phenoxysilane, monoethoxytrimethoxysilane, monobutoxytrimethoxysilane, monopentoxytrimethoxysilane, monohexoxytrimethoxysilane, dimethoxydiethoxysilane, dimethoxydibutoxysilane and the like. These can be used alone or in combination of two or more. The average condensation degree of (C) component becomes like this. Preferably it is 1-100, More preferably, it is about 4-20.

  As the component (C), (C-1) a condensate of alkoxysilane containing an alkoxyl group having 1 to 2 carbon atoms and an alkoxyl group having 3 to 12 carbon atoms (hereinafter referred to as “(C-1) It is desirable to use "components"). In particular, as the component (C-1), among the alkoxyl groups of the whole compound, those in which 5% by weight to 50% by weight are alkoxyl groups having 3 to 12 carbon atoms are preferable.

  Examples of the alkoxyl group having 3 to 12 carbon atoms include a direct group such as n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, and n-dodecyloxy group. Chain alkoxyl group, isopropoxy group, isobutoxy group, t-butoxy group, sec-butoxy group, isopentyloxy group, neopentyloxy group, isohexyloxy group, 3-methylpentyloxy group, 1-methylhexyloxy group, Examples include branched alkoxyl groups such as 1-ethylpentyloxy group, 2,3-dimethylbutoxy group, 1,5-dimethylhexyloxy group, 2-ethylhexyloxy group, 1-methylheptyloxy group, and t-octyloxy group. It is done.

  Such (C-1) component can be manufactured by a well-known method. Examples of the method for producing the component (C-1) include a method in which a tetraalkoxysilane condensate having an alkoxyl group having 1 to 2 carbon atoms is modified by an ester exchange reaction with an alcohol having 3 to 12 carbon atoms. Can be mentioned.

The mixing ratio of the component (C) is preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight in terms of SiO _{2 with} respect to 100 parts by weight of the resin solid content of the component (A). Less than parts by weight. When the component (C) is in such a range, an excellent contamination suppressing effect and the like can be obtained.

In addition, in terms of SiO ₂ in the present invention, the compound having a Si—O bond such as alkoxysilane is completely hydrolyzed and then burned at 900 ° C. to the remaining weight as silica (SiO ₂ ). It is expressed. In general, alkoxysilane reacts with water to cause a hydrolysis reaction to become silanol, and further has a property of causing a condensation reaction between silanols or between silanol and alkoxy. When this reaction is performed to the ultimate, silica (SiO ₂ ) is obtained. These reactions are
RO (Si (OR) ₂ O) _n R + (n + 1) H ₂ O → nSiO ₂ + (2n + 2) ROH (R represents an alkyl group. N is an integer.)
It is expressed by the reaction formula. The SiO ₂ conversion in the present invention is the conversion of the amount of the remaining silica component based on this reaction formula.

  The intermediate coating layer of the present invention is preferably formed by using an intermediate coating material comprising a main agent containing the component (A) and a curing agent containing the components (B) and (C). If it is such a form, the effect of this invention can be acquired stably. When the main agent and the curing agent are produced, the respective constituent components may be uniformly mixed by a conventional method.

The intermediate coating material of the present invention can contain a pigment in addition to the above-described components. As the pigment, general coloring pigments, extender pigments and the like can be used.
The mixing ratio of such a pigment is preferably 0.1 parts by weight or more and 200 parts by weight or less, more preferably 5 parts by weight or more and 150 parts by weight or less with respect to 100 parts by weight of the resin solid content of the component (A).

Examples of color pigments include titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, red potato, molybdate orange, permanent red, and permanent. Carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, first yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine, bitumen, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine Violet etc. are mentioned, These 1 type (s) or 2 or more types can be used. Moreover, an aluminum pigment, a pearl pigment, etc. can also be used.
Examples of extender pigments include heavy calcium carbonate, light calcium carbonate, kaolin, clay, porcelain clay, china clay, diatomaceous earth, hydrous finely divided silicic acid, talc, barite powder, barium sulfate, precipitated barium sulfate, barium carbonate, magnesium carbonate. , Silica powder, aluminum hydroxide, and the like, and one or more of these can be used.

  Various additive components can be mixed in the intermediate coating material as long as the effects of the present invention are not significantly impaired. Such components include, for example, film-forming aids, antifreeze agents, antiseptics, antifungal agents, antibacterial agents, antifoaming agents, dispersants, thickeners, leveling agents, wetting agents, pH adjusters, adsorption Agents, ultraviolet absorbers, antioxidants, catalysts, crosslinking agents and the like.

  The topcoat layer of the present invention is formed of a topcoat material containing (D) a fluororesin (hereinafter also referred to as “component (D)”). By using a fluororesin for the overcoat layer, excellent weather resistance, durability, chemical resistance, and the like can be obtained.

  As the component (D) in the present invention, various resins containing a fluorine atom in the resin skeleton can be used. Among these, as the component (D), a fluoroolefin copolymer is preferable. The fluoroolefin copolymer is a copolymer of a fluoroolefin and another copolymerizable monomer copolymerizable therewith. Examples of the fluoroolefin constituting the fluoroolefin copolymer include C2-C3 fluoroolefins such as tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinylidene fluoride, and vinyl fluoride. 1 type (s) or 2 or more types can be used.

  Examples of other copolymerizable monomers copolymerizable with fluoroolefin include vinyl ether, allyl ether, carboxylic acid vinyl ester, carboxylic acid allyl ester, ethylene, propylene, isobutylene, (meth) acrylic acid ester, and other various functional groups. The monomer etc. which have are mentioned, These 1 type (s) or 2 or more types can be used.

  Among these, examples of the vinyl ether include cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; alkyl vinyl ethers such as nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, and t-butyl vinyl ether. Examples of the allyl ether include alkyl allyl ethers such as ethyl allyl ether and hexyl allyl ether. Examples of the carboxylic acid vinyl ester or carboxylic acid allyl ester include vinyl esters or allyl esters of carboxylic acids such as acetic acid, butyric acid, pivalic acid, benzoic acid, and propionic acid.

  Examples of the monomer having a functional group include hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and cyclohexanediol monovinyl ether, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, and hydroxyalkyl vinyl crotonates. Hydroxyl group-containing monomers; carboxyl group-containing monomers such as crotonic acid and undecenoic acid; hydrolyzable silyl group-containing monomers such as triethoxyvinylsilane; epoxy group-containing monomers such as glycidyl vinyl ether and glycidyl allyl ether; aminopropyl vinyl ether and aminopropyl vinyl ether Monomers having an amino group such as;

  (D) As a component, the fluororesin which has a functional group which can react with the below-mentioned hardening | curing agent and can form a crosslink is preferable. The type of the functional group can be appropriately selected depending on the combination with the curing agent. Examples of such functional groups include hydroxyl groups, carboxyl groups, hydrolyzable silyl groups, epoxy groups, amino groups, and isocyanate groups. The method for introducing a functional group is not particularly limited, and examples thereof include a method of copolymerizing a monomer having a functional group, a method of introducing a functional group by a reaction after polymerization, and the like.

  As a method for introducing a functional group by a reaction after polymerization, for example, a method in which a hydroxyl group is introduced by saponifying a polymer copolymerized with a carboxylic acid vinyl ester, a polyvalent carboxylic acid or its anhydride is added to a polymer having a hydroxyl group. To introduce a carboxy group by reacting a product, to introduce a hydrolyzable silyl group by reacting an isocyanate alkylalkoxysilane to a polymer having a hydroxyl group, to react a polyvalent isocyanate compound to a polymer having a hydroxyl group Examples thereof include a method of introducing an isocyanate group.

  The number average molecular weight of the fluororesin is preferably from 2,000 to 100,000, more preferably from 6,000 to 30,000.

The fluorine content of the component (D) is preferably 15% to 40% by weight.
In addition, fluorine content in (D) component is a numerical value measured based on JISK5658: 2002.

  In addition to the component (D), the topcoat material includes (F) a curing agent component (hereinafter also referred to as the component (F)) having a functional group capable of reacting with the component (D) to form a crosslink. preferable.

  As the component (F), those capable of crosslinking with the component (D) at room temperature are suitable. As what reacts with (D) component at normal temperature, a polyisocyanate compound, a polybasic acid, etc. are mentioned, for example.

  Examples of the polyisocyanate compound include aliphatic polyisocyanate compounds such as ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, hexamethylene triisocyanate, and lysine diisocyanate, and fats such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, and diisocyanate methylcyclohexane. Examples thereof include cyclic polyvalent isocyanate compounds and non-yellowing aromatic isocyanate compounds such as m-xylene diisocyanate and p-xylene diisocyanate, and one or more of these can be used. Examples of the polybasic acid include long-chain aliphatic dicarboxylic acids, aromatic polyvalent carboxylic acids and acid anhydrides thereof.

  In the present invention, the (D) component is (D-1) a hydroxyl group-containing fluororesin (hereinafter also referred to as “(D-1) component”), and the (F) component is (F-1) a polyisocyanate compound (hereinafter referred to as “F”). , "(F-1) component"). If such (D-1) component and (F-1) component are used, effects, such as a weather resistance and crack resistance, can be improved further.

  As the component (D-1), a hydroxyl group-containing fluoroolefin copolymer is particularly suitable. The hydroxyl value of the component (D-1) is preferably 10 KOHmg / g or more and 200 KOHmg / g or less, more preferably 20 KOHmg / g or more and 100 KOHmg / g or less.

As the component (F-1), those having an isocyanate group content of 5 wt% or more (more preferably 9 wt% or more and 40 wt% or less, more preferably 12 wt% or more and 35 wt% or less) are suitable. .

  In this invention, it is preferable that the isocyanate group content of (F) component is larger than the isocyanate group content of (B) component. By having such a composition, while ensuring sufficient crack resistance, contamination by the plasticizer can be sufficiently suppressed by the dense cross-linked coating of the overcoat layer, and the effect of the present invention is further enhanced. Can do.

  The NCO / OH ratio of the hydroxyl group of the component (D-1) and the isocyanate group of the component (F-1) is preferably 0.3 or more and 2.0 or less, more preferably 0.6 or more and 1.5 or less. With such a ratio, the effect of the present invention can be further enhanced.

The topcoat material of the present invention may contain a resin component other than the component (D) and the component (F) as long as the effects of the present invention are not significantly impaired. Examples of the resin component other than the component (D) and the component (F) include alkyd resins, amino alkyd resins, polyester resins, epoxy resins, urethane resins, epoxy polyester resins, polyvinyl acetate resins, acrylic resins, vinyl chloride resins, phenols. Examples thereof include resins, silicone-modified polyester resins, acrylic silicone resins, and silicone resins.
These may contain a functional group capable of undergoing a crosslinking reaction with the component (F), such as a hydroxyl group, as long as the crosslinking reaction between the component (D) and the component (F) is not inhibited.

  The topcoat material of the present invention preferably contains (E) a tetraalkoxysilane compound (hereinafter referred to as component (E)). (E) component plays the role which hydrophilizes the surface of a laminated body and raises pollution resistance. By such an action of the component (E), the stain resistance due to prevention of plasticizer migration can be further enhanced, and excellent stain resistance can be obtained.

  As the component (E), the same component as the component (C) used in the intermediate coating layer can be used. In particular, a condensate having a degree of condensation of tetraalkoxysilane of 4 or more and 20 or less due to the early manifestation of surface hydrophilicity, and the alkyl group in the condensate has 1 to 2 carbon atoms and 3 to 10 carbon atoms. The tetraalkoxysilane low condensate is a compound in which the following are mixed, and the mixture ratio is an alkyl group having 3 to 10 carbon atoms in an amount of 5% by weight to 50% by weight of the total alkyl groups in the condensate. It can be preferably used.

The mixing ratio of the component (E) is usually 0.1 parts by weight or more and 50 parts by weight or less, preferably 1 part by weight or more and 30 parts by weight or less in terms of SiO _{2 with} respect to 100 parts by weight of the resin solid content of the component (D). It is. When the component (E) is in such a range, hydrophilicity is imparted to the coating surface, and excellent stain resistance can be obtained.

  The topcoat material of the present invention is preferably composed of a main agent containing the component (D) and a curing agent containing the component (E) and the component (F). If it is such a form, the effect of this invention can be acquired stably. When the main agent and the curing agent are produced, the respective constituent components may be uniformly mixed by a conventional method.

The topcoat material of the present invention can also contain various pigments. As the pigment, general color pigments, extender pigments and the like can be used, and for example, the same pigments as those for the intermediate coating layer can be used.
Furthermore, in the present invention, it is preferable that an infrared reflective powder is included as a pigment of the top coating material. If such an infrared reflective powder is contained, an excellent contamination suppressing effect can be obtained. Although the details are not clear, it is thought that the place where the plasticizer easily migrates as the temperature rises when exposed to sunlight is due to the suppression of the temperature rise by the infrared reflective powder.

Examples of the infrared reflecting powder include aluminum flake, titanium oxide, barium sulfate, zinc oxide, iron oxide, calcium carbonate, silicon oxide, magnesium oxide, zirconium oxide, yttrium oxide, indium oxide, alumina, and iron-chromium composite oxide. , Manganese-bismuth composite oxide, manganese-yttrium composite oxide, black iron oxide, iron-manganese composite oxide, iron-copper-manganese composite oxide, iron-chromium-cobalt composite oxide, copper-chromium composite oxide , Copper-manganese-chromium composite oxides, etc., and one or more of these can be used.

The mixing ratio of the pigment in the top coating material is preferably 0.1 parts by weight or more and 200 parts by weight or less, more preferably 5 parts by weight or more and 150 parts by weight or less with respect to 100 parts by weight of the resin solid content of the component (D).

  Various additive components can be mixed in the top coating material as long as the effects of the present invention are not significantly impaired. Such components include, for example, film-forming aids, antifreeze agents, antiseptics, antifungal agents, antibacterial agents, antifoaming agents, dispersants, thickeners, leveling agents, wetting agents, pH adjusters, adsorption Agents, ultraviolet absorbers, antioxidants, catalysts, crosslinking agents and the like.

  The laminate of the present invention can be used for surface finishing of various substrates such as concrete, mortar, siding board, extruded board, porcelain tile, metal, glass, plastic, etc., mainly for buildings, civil engineering structures, etc. Can be used to protect the enclosure.

  The laminate of the present invention can be applied directly to the base material, or can be applied after surface treatment of the base material in advance with a surface treatment material. When performing the surface treatment, any one or more of surface treatment materials such as a filler, a sealer, and a surfacer can be used.

The filler is mainly composed of inorganic powder such as cement, and if there are cracks or holes in the base material, it is repaired and adjusted by filling the part, and part or the whole surface of the base material as required. The base material is flattened by applying to the surface. The filler may contain a resin component.
The sealer is to improve the adhesion between the base material and the plasticizer-containing material by making the base material polar by applying a resin such as an epoxy resin as a main component and applying to a part or the entire surface of the base material. It is what makes it possible.
A surfacer has the functions of a filler and a sealer, and can be applied to a part of or the entire surface of the base material to improve the flatness and adhesion of the base material.

The method for applying the surface treatment material is not particularly limited, and spray coating, roller coating, brush coating, and the like can be appropriately employed. Drying is preferably performed at room temperature. Dabs amount of the surface treatment material, in the case of sealer, preferably 0.01 kg / ^{m 2} or more 1.0 kg / ^{m 2} or less, more preferably 0.05 kg / ^{m 2} or more 0.5 kg / ^{m 2} or less, surfacer, in the case of filler, preferably 0.1 kg / ^{m 2} or more 10.0 kg / ^{m 2} or less, more preferably 0.3 kg / ^{m 2} or more 5.0 kg / ^{m 2} or less.

  The laminate of the present invention can be obtained by sequentially laminating a plasticizer-containing material, an intermediate coating layer, and an overcoat layer on a substrate or a substrate subjected to the above surface treatment.

The construction method when the plasticizer-containing material is a waterproof coating material is not particularly limited, and a trowel, spatula, spray coating, roller coating, brush coating, or the like can be appropriately employed. It is preferable to dry the waterproof coating material at room temperature (-10 ° C to 50 ° C). The coating amount of the waterproof coating material is preferably 1.0 kg / m ² or more and 10.0 kg / m ² or less, more preferably 2.0 kg / m ² or more and 6.0 kg / m ² or less. With such a coating amount, a sufficient waterproof performance can be secured.
When the plasticizer-containing material is a sheet waterproof material, the sheet waterproof material may be bonded to the base material using an adhesive or the like.

The method for applying the intermediate coating material is not particularly limited, and spray coating, roller coating, brush coating, or the like may be employed as appropriate. Drying is preferably performed at room temperature. The coating amount of the intermediate coating material is preferably 0.05 kg / m ² or more and 1.0 kg / m ² or less, more preferably 0.1 kg / m ² or more and 0.5 kg / m ² or less. With such a coating amount, the effect of the present invention can be further enhanced.
The intermediate coating layer preferably does not contain a fluororesin. By not containing fluororesin in the intermediate coating layer, economical finishing is possible, and even if a long period of time elapses after the intermediate coating layer is applied, it is necessary to treat kelen etc. The topcoat layer can be laminated on the intermediate coating layer.

The method for applying the top coating material is not particularly limited, and spray coating, roller coating, brush coating, or the like may be appropriately performed. Drying is preferably performed at room temperature. The coating amount of the top coating material is preferably 0.05 kg / m ² or more and 1.0 kg / m ² or less, more preferably 0.1 kg / m ² or more and 0.5 kg / m ² or less. With such a coating amount, the effect of the present invention can be further enhanced.

  Examples are given below to clarify the features of the present invention.

<Inner coating material>
As the intermediate coating material, the raw materials shown in Table 1 were used.
The main agent used in the intermediate coating material was as shown in Table 2.
About the hardening | curing agent used with an intermediate coating material, what mix | blended the polyisocyanate compound 1 shown in Table 1 and the tetraalkoxysilane compound so that it might become 6: 1 weight ratio was made into the hardening | curing agent 1.
Curing agent 2 was prepared by blending polyisocyanate compound 2 and tetraalkoxysilane compound in a weight ratio of 6: 1.
Curing agent 3 was prepared by blending polyisocyanate compound 3 and tetraalkoxysilane compound in a weight ratio of 6: 1.
Curing agent 4 was prepared by blending polyisocyanate compound 4 and tetraalkoxysilane compound in a weight ratio of 6: 1.
Curing agent 5 was prepared by blending polyisocyanate compound 5 and tetraalkoxysilane compound in a weight ratio of 6: 1.
What used only the polyisocyanate compound 1 was made into the hardening | curing agent 6.

Table 3 shows combinations of the main agent and the curing agent in the intermediate coating materials 1 to 16.
The main agent and the curing agent were mixed so that the NCO / OH ratio was 1.0, and mixing was performed immediately before coating.

<Coating material>
As the top coat material, the raw materials shown in Table 4 were used.
The main agent used in the top coating material was as shown in Table 5.
About the hardening | curing agent used by topcoat material, what used only the polyisocyanate compound 6 shown in Table 4 was made into the hardening | curing agent A.
Curing agent B was prepared by blending polyisocyanate compound 6 and tetraalkoxysilane compound in a weight ratio of 6: 1.
Curing agent C was prepared by blending polyisocyanate compound 7 and tetraalkoxysilane compound in a weight ratio of 6: 1.
Curing agent D was prepared by blending polyisocyanate compound 8 and tetraalkoxysilane compound in a weight ratio of 6: 1.
Table 6 shows combinations of the main agent and the curing agent in the top coating materials 1 to 6.
The main agent and the curing agent were mixed so that the NCO / OH ratio was 1.0, and mixing was performed immediately before coating.

(Examples 1-19, Comparative Examples 1-3)
As a base material, a slate plate was coated with 0.1 kg / m ^{2 of an} epoxy resin sealer with a roller and dried at an air temperature of 23 ° C. and a relative humidity of 50% RH (hereinafter referred to as “standard state”) for 5 hours. Prepared.
A urethane rubber-based coating film waterproofing material (containing 10% by weight of a plasticizer) was applied to the base material using a trowel with 3.0 kg / m ² and dried in a standard state for 24 hours.
Next, an intermediate coating material was applied with 0.3 kg / m ² using a spray gun and dried in a standard state for 5 hours to form an intermediate coating layer.
Further, the top coat material was applied at 0.4 kg / m ² using a spray gun and dried in a standard state for 24 hours to form a top coat layer.
The test body was produced by the above method.
Table 7 shows the intermediate coating material and top coating material used in each Example and Comparative Example.

<Test 1>
The specimen was installed in Osaka Prefecture facing south at an angle of 30 degrees with respect to the horizontal plane, and the contamination resistance after exposure for 1 year and 2 years was evaluated. Evaluation was made into 5 grades, and it was excellent: 5>4>3>2> 1: poor.

<Test 2>
The test specimen was immersed in water at a temperature of 23 ° C. for 18 hours, then cooled at −20 ° C. for 3 hours, and heated at 50 ° C. for 3 hours. One cycle was repeated for 10 cycles, 20 cycles, and 30 cycles. Thereafter, the presence or absence of cracks on the surface of the coating and the surface state were confirmed. The evaluation was based on four grades (excellent: ◎>◯>Δ> ×: inferior), where ◎ indicates that no cracks were observed and × indicates that significant cracks occurred.

The results of Tests 1 and 2 are shown in Table 7.
As shown in this result, excellent contamination resistance is obtained in Examples 1 to 19 with respect to Comparative Examples 1 and 3. From this, it can be seen that the Examples of the present invention have improved contamination resistance due to the effect of preventing the migration of the plasticizer. Moreover, with respect to Comparative Example 2, Examples 1 to 19 have good crack resistance. From this, it can be seen that the laminate of the present invention has both the effect of preventing cracking and the effect of suppressing contamination.

Claims (4)

A laminate having an intermediate coating layer and a top coating layer on the surface of the plasticizer-containing material,
The intermediate coating layer is formed of an intermediate coating material containing (A) a polyol compound, (B) a polyisocyanate compound having an isocyanate group content of 5% by weight to 20% by weight, and (C) a tetraalkoxysilane compound. Layer,
The laminate is characterized in that the overcoat layer is a layer formed of (D) a topcoat material containing a fluororesin.   The laminate (A) according to claim 1, wherein the component (A) contains (A-1) a polyol compound having an amino group and / or a carboxyl group.   The layered product according to claim 1 or 2, wherein the component (A) contains (A-2) polycaprolactone diol and / or polycaprolactone triol. The laminate according to any one of claims 1 to 3, wherein the topcoat layer is formed of a topcoat material containing (D) a fluororesin and (E) a tetraalkoxysilane compound.