JP2003268323A - Adhesive sheet for outer wall of building - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive sheet for an outer wall of a building, which is excellent in a self-cleaning property, a lapping ability and a sealant adhesiveness. <P>SOLUTION: The sheet is produced by laminating (1) a peel-off layer, (2) an adhesive layer, (3) a base layer, (4) optionally a colored coat layer and (5) a clear coat layer in this order, wherein the clear coat layer (5) is formed by coating a composition using as a binder comprising (A) 100 wt. parts of a vinyl copolymer which comprises substantially a vinyl copolymer chain as a main chain and contains at least one hydrolyzable silyl groups bound to a carbon atom at terminal positions of the main chain and/or at side chains and at least one alcoholic hydroxy groups at terminal positions of the main chain and/or the side chains, (B) 1-70 wt. parts of a silicone compound and/or its partially hydrolyzed condensed material, (C) 0.01-10 wt. parts of an epoxysilane compound, (D) 1-100 wt. parts of a compound containing 2 or more isocyanate groups as a crosslinking agent, and (E) 0.01-10 wt. parts of an organic tin compound. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive
More specifically, the siloxane bond and urethane bond
The self-cleaning of stains, the lamination property and the
Outside construction with clear coating layer with excellent adhesive
The present invention relates to an adhesive sheet for a wall. [0002] 2. Description of the Related Art The outer walls of high-rise buildings and houses are
In recent years, the curtain wall method, the stone method, and the tile method
Often constructed by construction methods and used for these
Exterior building materials are contaminated by combustion products such as dust and exhaust gas.
And dirt eluted from the sealing material above,
Dirt due to pollutants discharged from the exhaust port overlaps
Rain streaks and darken, significantly impairing the aesthetics of the building
Therefore, the surface is usually coated with a coating to prevent contamination.
Has been applied. The coating agent for preventing contamination includes a repellent.
Has water repellency or self-cleaning property, weather resistance, durability, etc.
Is desirable, for example, fluororesin or silicone resin
Type, acrylic urethane type,
It is. Furthermore, from the viewpoint of shortening the man-hour, the coating
Plastics with a pollution control function
A method of attaching a film or sheet to the exterior building material
It has been proposed, especially for the modification of the outer wall constructed by the above method.
Useful when dressing. [0003] However, fluororesin and acrylic urethane
With a tan-based coating agent, dirt easily adheres over time
In the case of silicone resin, a film or sheet is attached
In the method of performing the lamination and the film
With a sealing material that fills the joints after attaching the sheet or sheet
There was a problem that the adhesion was poor. The purpose of the present invention is to
Suitable for sticking to exterior building materials,
Adhesion for building exterior walls with excellent adhesiveness and sealing adhesion
To provide a seat. [0004] SUMMARY OF THE INVENTION The present invention provides a release sheet.
Layer (1), adhesive layer (2), base sheet layer (3),
If necessary, colored coating layer (4) and clear coating layer
In the pressure-sensitive adhesive sheet obtained by sequentially laminating (5),
Coating layer (5) whose main chain is substantially a vinyl copolymer
Consisting of chains, at the ends and / or side chains of the main chain Formula (I): Embedded image (Where R¹Is a hydrogen atom or an alkyl having 1 to 10 carbon atoms
R group, R^TwoIs a hydrogen atom or an alkyl having 1 to 10 carbon atoms
Group, aryl group having 6 to 25 carbon atoms and 7 to 12 carbon atoms
A is a monovalent hydrocarbon group selected from the group consisting of
Represents an integer of 2 to 2)
When at least one decomposable silyl group is present in the molecule,
Alcoholic hydroxyl at the main chain terminal and / or side chain
(A) component of vinyl copolymer having at least one group
100 parts by weight, Formula (II): Embedded image (Where R^ThreeIs a hydrogen atom or an alkyl having 1 to 10 carbon atoms
Monovalent selected from an aryl group, an aryl group and an aralkyl group
A hydrocarbon group of R^FourIs an alkyl group having 1 to 10 carbon atoms,
A monovalent group selected from a reel group and an aralkyl group, b is 0
Or 1) and / or
Or its partial hydrolysis condensate (B) component 1 to 70 weight
Parts, epoxysilane compound (C) component 0.01 to 10 times
Parts, contains two or more isocyanate groups as a crosslinking agent
Compound (D) 1-100 parts by weight of component, organotin compound
(E) A resin composition comprising 0.01 to 10 parts by weight of a component
Apply clear paint composition as binder component to form
A pressure-sensitive adhesive sheet for building exterior walls characterized by being formed
You. [0007] BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a release sheet layer
(1) is one side of the pressure-sensitive adhesive layer (2) (which is opposite to the base sheet layer).
Located on the opposite side), for example, silicon, wax, fluorine
Paper or sheet treated with a release agent such as resin
It is a sheet showing body release properties. The thickness of the sheet is about 1
0 to 1000 μm, preferably about 20 to 250 μm.
It is an enclosure. In the present invention, the pressure-sensitive adhesive layer (2) has a releasability.
Located between the sheet layer (1) and the base sheet layer (3),
For example, natural rubber, acrylic resin, ethylene / vinyl acetate
Copolymer, polyurethane, polyester, silicone rubber
, Fluoro rubber, polyvinyl butyral, etc.
It is a layer formed of a known pressure-sensitive and heat-sensitive adhesive.
Such adhesives include, for example, tackifiers, tackifiers, anti-aging
Stoppers, stabilizers, coloring agents and the like can be included. The adhesion
The thickness of the agent layer (2) is about 10 to 1000 μm, preferably
Is preferably in the range of about 20 to 500 μm. As an adhesive
In particular, a pressure-sensitive adhesive is preferable. In the present invention, the base sheet layer (3) comprises:
Colored coating layer provided on the surface of the base sheet layer (3)
(4) Or fix the clear coating layer (5)
It is intended to be able to be attached to an adherend.
For example, aluminum, iron, stainless steel, tin, copper, etc.
Metal sheets; polyvinyl chloride resin, polyethylene tele
Phthalate resin, polyethylene resin, polyurethane tree
Fat, fluororesin, polypropylene resin, polystyrene
Fat, polycarbonate resin, polybutylene terephthalate
Plastic sheets such as resin; sheets made of paper, etc.
It is. As these base sheet layers (3),
German or combination, such as metal deposition, lamination
Even nates are acceptable. In addition these
The base sheet layer itself may be colored. The
The thickness of the base sheet layer (3) is about 5 for metal sheets.
~ 200 µm, preferably about 10-80 µm,
Approximately 5-2000 μm for plastic sheets and paper
More preferably, the range is about 10 to 1000 μm. In the present invention, the colored coating layer (4) is required
Is applied and provided on the base sheet (3) according to
Things. The thickness of the colored coating layer (4) is not particularly limited.
Although it is not a thing, usually 1 to 100 μm in dry film thickness
m, preferably in the range of 5 to 50 μm.
Appearance of Colored Coating Film, Prevents Waki (Foaming) of Coating Film During Drying
It is suitable in terms of stopping and the like. The colored coating is used
Depending on the type of paint or ink, leave at room temperature, heat,
Drying or curing
Can be. The coloring paint or ink used above is
For example, non-curing type, curing at room temperature or by heating
Molds, and even those that are cured by electron beam irradiation such as ultraviolet rays
Is included. Non-curing type, for example, the organic solvent evaporates
Is a composition that forms a dry coating film only by
Ester resin, alkyd resin, epoxy resin, vinegar
Vinyl acid resin, vinyl chloride resin, vinyl acetate / chloride
Vinyl copolymer resin, fluorine resin, urethane resin,
Riamide resin, silicone resin, rubber, and acrylic
And a resin containing a binder resin as a binder component.
As the hardening type, for example, an oxidation hardening type resin (alkyd resin)
Such as resins having oxidatively polymerizable unsaturated groups), moisture hardening
Resin (isocyanate group-containing acrylic resin or alcohol)
Xyloxy group-containing acrylic resin, etc.), multi-component reaction curing type
Resin (polyether polyol, polyester polyol
Hydroxyl, acrylic polyol, fluorine polyol, etc.
Polyisocyanate or melamine curing agent
Combined composition, unsaturated polyester resin and peroxide
Radical-curing resin, etc.)
As a binder component. Electron beam curing type
For example, acrylic resin, polyester resin, silicone resin
Electron for recon resin, polyether resin, fluorine resin, etc.
Those having a line-curable unsaturated group bonded to the binder component
To do. [0012] Coating of the above colored paint or ink (including printing)
As a method, a conventionally known method, for example, a sp
Ray painting, brush painting, roller painting and printing (screen
, Gravure, etc.)
Wear. Also, multi-nozzle spray gun, multi-head spray gun
Spray coating equipment with two or more discharge nozzles
It can also be used to form a multicolored coating film. In the present invention, the clear coating layer (5) comprises:
It provides self-cleaning properties to the exterior material surface.
Carbon sheet (3) or colored printed layer (4)
Hydrolyzable silyl groups attached to atoms and alcoholic water
Vinyl copolymer having acid group (A), silicon compound
And / or partial hydrolysis condensate thereof (B), epoxy
Sisilane compound (C), crosslinking agent (D) and organotin compound
A resin composition comprising (E) a binder component;
It is formed by applying a coating composition. the above
The main chain of the vinyl copolymer (A) is substantially a vinyl copolymer.
Consists of a polymer chain, generally at the terminal and / or side chain of the main chain
Formula (I): [0014] Embedded image(Where R¹Is a hydrogen atom or an alkyl having 1 to 10 carbon atoms
R group, R^TwoIs a hydrogen atom or an alkyl having 1 to 10 carbon atoms
, A monovalent carbon selected from an aryl group and an aralkyl group
A hydride group, a represents an integer of 0 to 2)
Hydrolyzable silyl groups (including silanol groups)
Is at least one in one molecule, and
Fewer alcoholic hydroxyl groups at main chain terminals and / or side chains
It is a vinyl copolymer having at least one. The copolymer
The body consists essentially of a vinyl copolymer chain in its main chain
The resulting clear coating has excellent weather resistance and chemical resistance
And a hydrolyzable silyl group.
Is bonded to the carbon atom, so the coating has excellent water resistance,
It can impart alkali resistance, acid resistance and the like. In the above component (A), the compound represented by the general formula (I)
If the number of the hydrolyzable silyl group represented is one or more in the molecule,
Good, but said that the resulting clear coating has excellent solvent resistance
From this point, it is preferable to have 2 to 10 pieces. The above general formula
In (I), R¹Is a hydrogen atom or 1 to 10 carbon atoms
And preferably an alkyl group such as a methyl group,
Tyl group, n-propyl group, i-propyl group, n-butyl
Groups having 1 to 4 carbon atoms, such as
Is a alkyl group. The alkyl group has more than 10 carbon atoms
, The reactivity of the hydrolyzable silyl group decreases.
There is a tendency. In addition, the R¹Is, for example, a phenyl group,
And other groups other than alkyl groups such as
It is not preferable because the reactivity of the decomposable silyl group decreases. In the above general formula (I), R^TwoIs
A hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
More preferably, the R¹Has 1 to 1 carbon atoms as shown in the specific examples.
Ants having 6 to 25 carbon atoms such as alkyl group 4 and phenyl group
Aralkyl groups having 7 to 12 carbon atoms, such as
Are monovalent hydrocarbon groups selected from
Is an alkyl from the viewpoint that the resulting coating film has excellent curability.
Preferred is a phenyl group. Alcohol in the vinyl copolymer (A)
Hydroxyl equivalents (one mole containing alcoholic hydroxyl groups)
The amount (g) of the phenyl-based copolymer is 300 to 3,000 g.
/ Mol is preferred. More preferably, 500 to
2500 g / mol, particularly preferably from 700 to 2,000
00 g / mol. Hydroxyl equivalent is less than 300 g / mol
Storage stability of the resulting clear coating composition
And the clear coating film have insufficient acid resistance.
If it exceeds 0 g / mol, the curability tends to be poor.
You. The vinyl copolymer (A) is, for example,
Polymerizing a copolymer component containing (i) to (iii) and the like
Can be manufactured. (I) Hydrolyzable silyl group-containing vinyl monomer (monomer
(A-1)), (ii) hydroxyl group-containing vinyl monomer (mono)
(A-2)), (iii) Other copolymerizable single monomers
Body (monomer (a-3)). The monomer (a-1) and
For example, the following may be mentioned. [0019] Embedded image General formula (III) such as [0020] Embedded image (Where R^FiveRepresents a hydrogen atom or a methyl group;
⁶Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
An aryl group having 6 to 10 or an ara having 7 to 10 carbon atoms
Represents a alkyl group, and when there are a plurality of
May also be different. R⁷Is alk having 1 to 10 carbon atoms
A plurality of groups, and when multiple
It may be. a represents an integer of 0 to 2. )
Compound to be used; [0021] Embedded imageGeneral formula (IV) such as [0022] Embedded image (Where R^Five, R⁶, R⁷, A is the same as above, and n is 1 to
Indicates an integer of 12. A) a compound represented by the formula: [0023] Embedded image General formula (V) such as: [0024] Embedded image (Medium, R^Five, R⁶, R⁷, A and n are the same as described above)
Compound; [0025] Embedded image General formula (VI) such as: [0026] Embedded image (Where R^Five, R⁶, R⁷And a are the same as above, and p is 1
A compound represented by the general formula:
The hydrolyzable silyl group represented by (I) is
Or a (meth) acyl compound having a terminal through a siloxane bond.
Related, etc. These may be used alone or in combination of two or more.
You may use together. Among them, easy to handle and low
Price and the absence of reaction by-products
The compound represented by the general formula (V) is preferred. The amount of the monomer (a-1) used is determined by
5 to 60% (% by weight, hereinafter the same) of the total amount is preferable,
More preferably, it is 10 to 50%. Such a monomer
When the amount of (a-1) used is less than 5%,
The acid resistance of the clear coating film tends to be insufficient,
If it exceeds 60%, the storage stability of the composition decreases.
Tend to be. Next, as the monomer (a-2),
For example, 2-hydroxyethyl (meth) acrylate,
1-hydroxypropyl (meth) acrylate, 2-h
Droxypropyl (meth) acrylate, 2-hydroxy
Siethyl vinyl ether, N-methylol (meth) ac
Lilamide, Aronix 5700 (Toa Gosei Chemical Industry)
4-hydroxystyrene, HE-10, H
E-20, HP-1, HP-20, etc.
Acrylate oligomers
Gaku Kogyo Co., Ltd.), Blemmer PP series (Polypro
Pyrene glycol methacrylate), Blemmer PE
Leeds (Polyethylene glycol monomethacrylate)
G), Blemmer PEP series (polyethylene glyco)
Polypropylene glycol methacrylate), blur
Nmmer AP-400 (polypropylene glycol monoa
Acrylate), Blemmer AE-350 (polyethylene)
Glycol monoacrylate), Blemmer NKH-5
050 (polypropylene glycol polytrimethylene
Acrylate), Blemmer GLM (glycerol
Nomethacrylate) (Nippon Yushi Co., Ltd.)
), Hydroxyl-containing vinyl compound and ε-caprolactone
Ε-caprolactone-modified hydro obtained by the reaction of
Xyalkyl vinyl copolymerizable compounds and the like can be mentioned.
Further, the ε-caprolactone-modified hydroxyalkyl
Representative examples of vinyl copolymerizable compounds include, for example, general
Formula (VII): [0029] Embedded image The compound represented by is mentioned. As a specific example,
For example, PlacelFA-1 (R^FiveIs a hydrogen atom, q is
1), Placel FA-4 (R^FiveIs a hydrogen atom, q
4), Placel FM-1 (R^FiveIs a hydrogen atom,
q is 1), Placel FM-4 (R^FiveIs hydrogen field
, Q is 4) (these are Daicel Chemical Industries, Ltd.), T
ONE M-100 (R^FiveIs a hydrogen atom, q is 2), TO
NE M-201 (R^FiveIs a methyl group, q is 1),
And UCC). These monomers
(A-2) may be used alone or in combination of two or more.
Is also good. Among the above monomers (a-2), the obtained
That the clear coating film has excellent acid resistance and water resistance
From 2-hydroxypropyl (meth) acrylate,
2-hydroxyethyl (meth) acrylate and ε-
Caprolactone-modified hydroxyalkyl vinyl copolymer
Compounds are preferred, especially 2-hydroxypropyl (meth
Ta) Acrylates are preferred. The monomer (a-2)
Is preferably 0 to 50% of the total amount of the copolymer components,
More preferably, it is 2 to 35%. Such a monomer
-When the usage of (a-2) exceeds 50%,
And Acid Resistance of Coating Films Formed Using Neutral Compositions
Tends to decrease. As the monomer (a-3), for example,
Methyl (meth) acrylate, ethyl (meth) acryle
, N-butyl (meth) acrylate, isobutyl
(Meth) acrylate, 2-ethylhexyl (meth) a
Acrylate, stearyl (meth) acrylate, benzyl
(Meth) acrylate, cyclohexyl (meth) acryl
Relevant, trifluoroethyl (meth) acrylate,
Pentafluoropropyl (meth) acrylate, perf
Fluorocyclohexyl (meth) acrylate, (meth)
Acrylonitrile, glycidyl (meth) acrylate,
Dimethylaminoethyl (meth) acrylate, diethyl
Aminoethyl (meth) acrylate, (meth) acryl
Amide, α-ethyl (meth) acrylamide, N-methyl
(Meth) acrylamide, N, N-dimethyl (meth)
Acrylamide, N-butoxymethyl (meth) acryl
Amides, macromonomers AS-6, AN-6, A
Compounds such as A-6, AB-6, and AK-5
Seikagaku Kogyo Co., Ltd.), (meth) acrylic acid hydroxy
Α, β-ethylenically unsaturated esters such as silalkyl esters
Hydroxyalkyl esters of rubonic acid and phosphoric acid or
Is a phosphate ester such as a condensation product with a phosphate ester
Group-containing vinyl compound, urethane bond or siloxane bond
(Meth) acrylic acid such as (meth) acrylate containing
Conductor, styrene, α-methylstyrene, chlorostyrene
Styrene, styrenesulfonic acid, 4-hydroxystyrene, vinyl
Aromatic hydrocarbon vinyl compounds such as nyltoluene; male
Unsaturated carboxylic acids such as formic acid, fumaric acid, itaconic acid,
These alkali metal salts, ammonium salts, amine salts, etc.
Salts of unsaturated carboxylic acids such as maleic anhydride
Having a linear or branched chain having 1 to 20 carbon atoms.
Diester or half ester with alcohol
Esters of unsaturated carboxylic acids of vinyl; vinyl acetate, propio
Vinyl esters such as vinyl acid and diallyl phthalate;
Allyl compound; vinylpyridine, aminoethyl vinyl ether
Amino-containing vinyl compounds such as ether; di-itaconate
Amide, crotonamide, maleic diamide, fumaric
Amide group-containing resins such as acid diamide and N-vinylpyrrolidone
Nyl compounds: methyl vinyl ether, cyclohexyl
Vinyl ether, vinyl chloride, vinylidene chloride, chloro
Prene, propylene, butadiene, isoprene, fluoro
Polyolefin maleimide, N-vinylimidazole,
And other vinyl compounds such as nylsulfonic acid.
It is. These may be used alone or in combination of two or more.
Is also good. The monomer (a-3) is an amide
With carboxylic, sulfonic, or phosphoric acid groups
When a reactive monomer is used, the crosslinking reaction during polymerization is suppressed.
Therefore, the amount used should be 5% or less of the total amount of the copolymer components.
It is desirable to do so. In the present invention, the obtained
Improved weather resistance, solvent resistance, bending resistance, etc. of the rear coating film
Range not to exceed 50% of the vinyl copolymer
And is formed by urethane bond or siloxane bond.
To be contained in the main chain of the vinyl copolymer.
May be used. The vinyl copolymer used in the present invention is:
Monomer (a-1), monomer (a-2), monomer
-(A-3) and other copolymer components containing, for example,
JP-A-54-36395, JP-A-57-55954
It can be manufactured by the method described in the gazette, etc.,
Azobisisobutyronitrile, etc. in terms of ease of synthesis
Solution polymerization using azo radical polymerization initiator
It is preferable to manufacture it. The polymerization solvent used in the solution polymerization method is as follows:
Any non-reactive material is acceptable, and there is no particular limitation.
Toluene, xylene, n-hexane, cyclohexane
Hydrocarbons such as ethyl acetate, butyl acetate, etc.
Ters; methanol, ethanol, isopropanol,
alcohols such as n-butanol; ethyl cellosolve;
Ethers such as butyl cellosolve and cellosolve acetate
Classes: methyl ethyl ketone, ethyl acetoacetate, acetyl
Acetone, diacetone alcohol, methyl isobutyl ketone
And ketones such as acetone and acetone. The above-mentioned polymerization solvent may be used alone,
More than one species may be used in combination, but methanol or
The amount of alcohols, such as ethanol, is
If the amount is less than 1 part, gelation may occur during polymerization.
100 parts of the copolymer component in the polymerization solvent
Alcohol is contained in a ratio of 1 to 30 parts with respect to
It is preferable to do so. In addition, during the solution polymerization,
Vinyl copolymers obtained by using chain transfer agents
The molecular weight of the body may be adjusted. Specific examples of the chain transfer agent include, for example,
n-dodecyl mercaptan, tert-dodecyl merca
Butane, n-butyl mercaptan, γ-mercaptopro
Piltrimethoxysilane, γ-mercaptopropyltri
Ethoxysilane, γ-mercaptopropylmethyldimethoate
Xysilane, γ-mercaptopropylmethyldiethoxy
Silane, (CH_ThreeO)_ThreeSi-SS-Si (OC
H_Three)_Three, (CH_ThreeO)_ThreeSi-S₈-Si (OCH_Three)_Threeetc
Is mentioned. These may be used alone or in combination of two or more.
You may use together. For example, the γ-mercaptopropyl trim
Has a hydrolyzable silyl group such as toxicsilane in the molecule
When a chain transfer agent is used, the main chain of the vinyl copolymer
Since a hydrolyzable silyl group can be introduced at the terminal
preferable. The amount of the chain transfer agent used depends on the copolymerization component.
On the other hand, it is preferably about 0.1 to 10%. The present invention
With the components for improving the stain resistance of the clear coating,
The following general formula (II): [0038] Embedded image (Where R^ThreeIs an alkyl group having 1 to 10 carbon atoms and 6 carbon atoms
Aryl group having 10 to 10 and aralkyl having 7 to 12 carbon atoms
A monovalent hydrocarbon group selected from^FourIs carbon number 1 to 1
0 alkyl group, aryl group having 6 to 10 carbon atoms and carbon
Monovalent hydrocarbon selected from aralkyl groups having a prime number of 7 to 12
Element group, b represents 0 or 1) silicon compound and / or
Or its partially hydrolyzed condensate (B) (hereinafter referred to as silicon
Compound (B)) can also be used. Shi
Recon compound (B) adheres clear coating layer to lower layer
Can be used as a component to improve
You. Silicone compound (B) is vinyl copolymer (A)
Is mixed with a room temperature curable composition,
The clear coating film formed using the composition has excellent resistance to
Stain properties, but the coating has excellent stain resistance
The reason is not yet clear. Probably acrylic
Relative between copolymer (A) and silicon compound (B)
Due to differences in curing speed and compatibility, surface hardness and hydrophilicity
It is considered that the improvement of the performance has an effect. In the general formula (II), R^ThreeIs carbon
Formulas 1 to 10, preferably, for example, a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
An alkyl group having 1 to 4 carbon atoms such as a butyl group, preferably
For example, an aryl group having 6 to 9 carbon atoms such as a phenyl group,
Preferably, an alkyl group having 7 to 9 carbon atoms such as a benzyl group is used.
It is a monovalent hydrocarbon group selected from aralkyl groups. Said
If the alkyl group has more than 10 carbon atoms, silicon
The reactivity of the compound (B) decreases. Also,
R^ThreeIs other than the above-mentioned alkyl group, aryl group and aralkyl group
In this case, the reactivity also decreases. In the general formula (II), R^Four
Represents 1 to 10 carbon atoms, preferably R^Three1 to 1 carbon atoms
4 alkyl groups, preferably R^Three6-9 carbon atoms similar to
Aryl group, preferably R^ThreeWith 7 to 9 carbon atoms
It is a monovalent hydrocarbon selected from aralkyl groups. In the general formula (II), (R^ThreeO)
_4-bIs such that 4-b is 3 or more, that is, b is 0 or less.
Or 1 but the curability of the clear coating
From the viewpoint that b is improved, it is preferable that b is 0.
No. (R) present in the general formula (II)^ThreeO)_4-bIs 2
In the case of two or more R^ThreeIs the same
Well, they can be different. Specific examples of the general formula (II) include:
For example, tetramethyl silicate, tetraethyl silicate
, Tetra n-propyl silicate, tetra i-propyl
Rusilicate, tetra n-butyl silicate, tetra i
-Tetraalkyl silicates, such as butyl silicate;
Methyltrimethoxysilane, methyltriethoxysila
Phenyltrimethoxysilane, phenyltriethoxy
Sisilane, octadecyltriethoxysilane, 3-gri
Sidoxypropyltrimethoxysilane, methyltrise
c-octyloxysilane, methyltriphenoxysila
, Methyltriisopropoxysilane, methyltribute
Silane coupling agents such as xysilane;
You. Further, specific examples of the silicon compound and the like (B)
Examples include, for example, the tetraalkyl
Add water to silicate or trialkoxysilane and condense
Examples thereof include those obtained by MSi51,
MSi53, ESi28, ESi40, HAS-1, H
AS-10, EMS30 / 70 or EMS40 / 60 or E
EMS series such as MS485, EPSi series (hereinafter
Upper, manufactured by Colcoat Co., Ltd.), MS51, MS56, MS
51B15, MS56S, MS56SB5 (Mitsubishi
Chemical Co., Ltd.), silicate 40, silicate 45, silicon
Like 48, FR-3, mih028, mih032
(Above, manufactured by Tama Chemical Co., Ltd.)
Partially hydrolyzed condensate of kate, for example, AFP-1
Trialkoxysilanes (Shin-Etsu Chemical Co., Ltd.)
And the like. Among the above silicon compounds (B),
Compatibility with vinyl copolymer (A), resulting clear
Good curability of coating film and excellent hardness of coating film
From MSi51, MS51, MS56, MS51B1
5, MS56S, MS56SB5 (tetramethoxysila
Partial hydrolysis and condensation products), ESi40, silicate 4
0, silicate 45, silicate 48, ESi 48 (te
Partially hydrolyzed condensate of traethoxysilane), FR-
3. EMS series (Tetramethoxysilane and TetraE
Tetraa such as co-hydrolyzed condensate of toxicoxysilane)
It is preferable to use a partially hydrolyzed condensate of alkyl silicate.
Good. Furthermore, the silicon compound and the like (B)
MS56 and MS56S with high degree of condensation, silicate
45, silicate 48ESi48, FR-3, EMS
Does the series etc. lower the contact angle from the beginning?
Are preferred. The amount of the component (B) used is 100 parts of the component (A).
1 to 70 parts, preferably 5 to 70 parts, more preferably
Preferably, it is 10 to 50 parts. Less than 1 part of component (B)
In some cases, the effect of stain resistance is not sufficient, and exceeds 70 parts.
In this case, the bending resistance and the sealant adhesion are reduced. The epoxysilane compound (C) is
Improves the adhesiveness in the case of affixing a light adhesive sheet
Used to Specifically, β- (3,4-ep
(Xycyclohexyl) ethyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane and the like.
You. These epoxysilane compounds (C) may be used alone or
Can be used in combination. (C) Component distribution
The total amount is 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight.
1 to 5 parts by weight, more preferably 0.5 to 5 parts by weight
You. [0047] The resin composition contains the component (A)
Compound having two or more isocyanate groups as a crosslinking agent
(D) component is contained. Two or more isocyanate groups
As the compound to have, aliphatic or aromatic compounds
Things. Of aliphatic polyfunctional isocyanates
As a specific example, hexamethylene diisocyanate is used for curing at room temperature.
Nath, dicyclohexylmethane 4,4'-isocyanana
ト, 2,2,4-trimethyl-1,6-diisocyanana
And isophorone diisocyanate.
Monomer, buret type, urezio type, isocyanurate
-There is a type. For heat curing, block type
There is. Methyl alcohol, e.
Tyl alcohol, n-propyl alcohol, iso-pro
Pill alcohol, n-butyl alcohol, sec-butyl
Ru alcohol, methyl cellosolve, ethyl cellosolve,
Butyl cellosolve, benzyl alcohol, furfurylua
Alcohol, cyclohexyl alcohol, phenol, o
-Cresol, m-cresol, p-cresol, p-
tert-butylphenol, thymol, p-nitrophenol
Phenol and β-naphthol. In addition, aromatic
Functional isocyanates include 2,4-tolylenediamine
Socyanate, 2,6-tolylene diisocyanate, di
Phenylmethane-4,4'-diisocyanate, xylene
Diisocyanate, polymethylene-polyphenylene-
And polyisocyanates. This also includes
, Uresio and isocyanurate types. these
Can be used as a mixture of two or more. Use of the above isocyanate compound (D)
The dose is 1 to 100 parts by weight based on 100 parts by weight of the component (A).
Parts by weight, preferably 5 to 80 parts by weight, more preferably 10 parts by weight.
To 60 parts by weight. (D) When the component is less than 0.1 part
In such a case, the curability of the obtained clear coating film may decrease.
When the amount exceeds 100 parts, unreacted iso-
A cyanate compound or an isocyanate group remains,
May cause poor weather resistance and blemishes during recoating
It is not preferred. The organotin compound (E) is clear
Used as a curing catalyst to improve the curability of the coating
It is. Especially, in consideration of storage stability and curing activity,
Compounds having an S atom are preferred. A specific example of the organotin compound is dioctane.
Chill tin bis (2-ethylhexyl maleate), dioctyl
Tin oxide or dibutyltin oxide and silica
Condensates with dibutyltin, dibutyltin dioctoate, dibutyltin
Dilaurate, dibutyltin distearate, dibutyltin
Diacetylacetonate, dibutyltin bis (ethyl maleate)
-T), dibutyltin bis (butyl maleate), dibutyl
Tin bis (2-ethylhexyl maleate), dibutyltin
(Oleyl maleate), stannase octoate,
Tin arsenate, di-n-butyltin rallate oxide
is there. Further, as a tin compound having an S atom in the molecule,
Dibutyltin bisisononyl-3-mercaptopropione
-Dioctyltin bisisononyl-3-mercaptop
Lopionate, octylbutyltin bisisononyl-3-
Mercaptopropionate, dibutyltin bisisooctyl
Luthioglucolate, dioctyltin bisisooctylchi
Oglucolate, octylbutyltin bisisooctylchi
Oglucolate and the like. Among the above organotin compounds, S is contained in the molecule.
When the compound having atoms contains isocyanate
Storage stability and pot life
And especially dibutyltin bisisononyl-3-mercap
Dibutyltin bisisooctylthioglucorate is hard
It is preferable from the viewpoint of balance between chemical properties, storage stability, and pot life.
No. The organotin compound (E) may be used alone.
And two or more of them may be used in combination. The component (E)
Is used in an amount of 0.01 to 100 parts by weight of the component (A).
To 10 parts by weight, preferably 0.1 to 8 parts by weight, more preferably
The preferred amount is 0.3 to 5 parts by weight. In addition, organotin compounds
When the amount of the component (E) exceeds 10 parts, the resulting clear
ー The appearance of the coating, such as surface gloss, tends to decrease.
Is not preferred. The resin composition is a vinyl copolymer
(A) component, silicon compound and / or partial addition thereof
Hydrolysis condensate (B) component, epoxysilane compound (C)
Component, isocyanate compound (D) component, organotin compound
(E) A homogeneous composition is prepared by using, for example, a stirrer or the like.
Can be obtained by stirring and mixing so that
Although it is possible, the components (A) and (B) are further dehydrated.
, The storage stability of the composition is prolonged.
Can be excellent over time. Specific examples of the dehydrating agent include, for example, ortho
Methyl formate, ethyl orthoformate, methyl orthoacetate,
Ethyl acetate, trimethyl orthopropionate,
Triethyl topropionate, ortho-isopropionate
Limethyl, triethyl orthoisopropionate, ortho
Trimethyl butyrate, triethyl orthobutyrate, orthoisobutyrate
Water, such as trimethyl acrylate and triethyl orthoisobutyrate
A decomposable ester compound; or dimethoxymethane, 1,
1-dimethoxyethane, 1,1-dimethoxypropane,
1,1-dimethoxybutane; or ethyl silicate
(Tetramethoxysilane), methyl silicate (tetra
Methoxysilane), methyltrimethoxysilane, etc.
I can do it. Among them, from the viewpoint of dehydration effect, orthoacetic acid
Methyl is preferred. These may be used alone or in two types.
These may be used in combination. The dehydrating agent comprises the components (A) and (B)
100 parts or less, preferably 50 parts per 100 parts
Parts or less, more preferably 30 parts or less. Ma
In addition, the component (A) may be added to the component before polymerization,
(A) may be added during the polymerization of the component, and
(A) It may be added at the time of mixing the component with other components.
There is no particular limitation. Further, a clear coating composition containing the above resin composition
Compositions include, for example, pigments commonly used in paints;
Agents; diluents, ultraviolet absorbers, light stabilizers, anti-sagging agents,
Additives such as belling agents; nitrocellulose, cellulose
Fibrous materials such as acetate butyrate; epoxy resin;
Melamine resin, vinyl chloride resin, fluororesin, chlorinated resin
Propylene, chlorinated rubber, polyvinyl butyral, poly
Resins such as siloxane may be appropriately added. Coating of the clear coating composition (including printing)
As a method, a conventionally known method, for example, a sp
(Layers, brushes, rollers, etc.) and printing (screens,
Via, etc.). film
The thickness is about 0.1 to 50 μm, particularly about 1 to 30 in terms of cured film thickness.
The range of μm is preferred. In addition, curing is possible at room temperature.
There is usually curing in the heating range of 40-200 ° C
be able to. The pressure-sensitive adhesive sheet of the present invention obtained as described above
Is mainly used for curtain wall method, stone method, tile
Suitable for building exterior walls formed by tensioning or other methods
Used. As the building material of the building outer wall, for example, acrylic
Resin, polycarbonate resin, vinyl chloride resin, polyether
Steal resin, heat-resistant engineering plastic, various types
Plastic panels such as thermosetting resin; cement, gas
Ceramic panel such as lath fiber reinforced slate; iron-based,
Aluminum, magnesium and titanium metals
Panels and further chemical conversions of these metals; glass
Panel (heat ray reflective glass or crystallized glass), high strength core
Concrete, glass fiber reinforced concrete (GRC),
Carbon fiber reinforced concrete, lightweight cellular foam concrete
(ALC) Concrete panel; tile, natural stone board, none
Machine siding material, enameled iron plate, painted steel plate, window frame sash
And the like. The adhesive sheet of the present invention is usually attached
Performed after the surface treatment of the building material
Sealant such as silicone on the joint between building materials
Fill. In the case of renovation of the building outer wall,
Remove existing sealing material such as ground and seal around
Removes dirt from the ring material, eluted oil and soot.
For metal surfaces, remove rust and remove dents
Process with putty or the like accordingly. Next, the coating layer on the building material side is polished.
And apply the sheet, and finally,
Filling the ground with a silicone-based sealing material
You. [0059] The present invention will be described in more detail with reference to the following examples.
As will be described, the present invention is limited to only such an embodiment.
is not. “Parts” and “%” are “parts by weight” and
And "% by weight". [0060]Manufacture of resin for clear paint Production Example 1 (Production of resin (A-1) component) Stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and drops
40 parts of xylene was charged into a reactor equipped with a lower funnel,
The temperature was raised to 110 ° C. while introducing a raw gas. Then, γ-
Methacryloxypropyltrimethoxysilane 20 parts, 2
-Hydroxyethyl methacrylate 13 parts, methyl meth
22 parts of acrylate, 18 parts of n-butyl methacrylate,
n-butyl acrylate 12 parts, styrene 15 parts, xy
18 parts of ren and 2,2'-azobisisobutyronitrile
Of the mixture consisting of 3.8 parts by dropping funnel for 5 hours.
And dripped at a constant speed. After completion of the dropping, 2,2'-azobisui
0.2 part of sobutyronitrile and 8 parts of toluene for 1 hour
And then stirred at 110 ° C for 2 hours.
After cooling, add xylene to the resin solution
A resin (A-1) solution having a concentration of 50% was obtained. The resulting tree
The number average molecular weight of Fat (A-1) was 6,300. Production Example 2 (Production of resin (A-2) component) Stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and drops
40 parts of xylene was charged into a reactor equipped with a lower funnel,
The temperature was raised to 110 ° C. while introducing a raw gas. Then, γ-
14 parts of methacryloxypropyltrimethoxysilane, 2
-Hydroxyethyl methacrylate 13 parts, methyl meth
25 parts of acrylate, 18 parts of n-butyl methacrylate,
15 parts of n-butyl acrylate, 15 parts of styrene,
18 parts of ren and 2,2'-azobisisobutyronitrile
Of the mixture consisting of 3.8 parts by dropping funnel for 5 hours.
And dripped at a constant speed. After completion of the dropping, 2,2'-azobisui
0.2 part of sobutyronitrile and 8 parts of toluene for 1 hour
And then stirred at 110 ° C for 2 hours.
After cooling, add xylene to the resin solution
A resin (A-2) solution having a concentration of 50% was obtained. The resulting tree
The number average molecular weight of Fat (A-2) was 6,000. Production Example 3 (Production of resin (A-3) component) Stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and drops
40 parts of xylene was charged into a reactor equipped with a lower funnel,
The temperature was raised to 110 ° C. while introducing a raw gas. Then, γ-
6.5 parts of methacryloxypropyltrimethoxysilane,
13 parts of 2-hydroxyethyl methacrylate, methyl methyl
29 parts of acrylate, n-butyl methacrylate 18
Parts, n-butyl acrylate 18.5 parts, styrene 15
Part, xylene 18 parts and 2,2'-azobisisobutyi
A mixture consisting of 3.8 parts of onitrile was dropped by a dropping funnel.
The solution was dropped at a constant speed over 5 hours. After the completion of the dropping, 2,2'-A
0.2 parts of zobisisobutyronitrile and 8 parts of toluene
Is added dropwise at a constant speed over 1 hour, and then at 110 ° C. for 2 hours.
Stir for a while, cool, add xylene to the resin solution
A resin (A-3) solution having a fat solid content of 50% was obtained. Profit
The number average molecular weight of the obtained resin (A-3) was 6,200.
Was. Production Example 4 (Production of resin (A-4) component) Stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and drops
40 parts of xylene was charged into a reactor equipped with a lower funnel,
The temperature was raised to 110 ° C. while introducing a raw gas. Then, γ-
11 parts of methacryloxypropyltrimethoxysilane,
42 parts of chill methacrylate, n-butyl acrylate
31 parts, styrene 15 parts, N-methylolacrylamide
, Xylene 18 parts and 2,2'-azobisisobutyi
A mixture consisting of 3.8 parts of onitrile was dropped by a dropping funnel.
The solution was dropped at a constant speed over 5 hours. After the completion of the dropping, 2,2'-A
0.2 parts of zobisisobutyronitrile and 8 parts of toluene
Is added dropwise at a constant speed over 1 hour, and then at 110 ° C. for 2 hours.
Stir for a while, cool, add xylene to the resin solution
A resin (A-4) solution having a fat solid content of 50% was obtained. Profit
The number average molecular weight of the resin (A-4) was 6,100.
Was. The number average molecular weight is determined by gel permeation
Chromatography analyzer (Toyo Soda Co., Ltd., HLC
Gel permeation chromatography using -8020
It was measured by performing luffy. [0064]Creating clear paint Creation example 1 Resin solid content 1 of resin (A-1) solution obtained in Production Example 1
With respect to 00 parts, as a component (B) such as a silicon compound, MS
56 (part of tetramethoxysilane manufactured by Mitsubishi Chemical Corporation)
Hydrolysis condensate) 10 parts, epoxy silane 2 parts, S raw
Dibutyltin bisisono as a tin-containing tin catalyst (E) component
One part of nil-3-mercaptopropionate was added, and
And 1 part of mercaptosilane as a curing regulator,
Hexamethylenediiso as an anate compound (D) component
20 Cyanate Nurate Structures (Coronate HX)
Parts by weight, and further added Tinuvin 384 (Ciba-geigy-
Co., Ltd. UV absorber) 2 parts and Tinuvin 292 (H
Bagaigi Co., Ltd. light stabilizer). this
Dilute the mixture with xylene to clear 40% solids
-Paint was created. Preparation Examples 2 to 7 and Comparative Preparation Examples 1 to 4 Except that the clear paint was adjusted according to the formulation shown in Table 1.
Prepared each clear paint in the same manner as in Preparation Example 1.
Was. [0066] [Table 1][0067]Making adhesive sheet Example 1 Adhesive plastic film (vinyl chloride 50μm,
On the vinyl chloride surface of the cryl adhesive (10 μm),
The clear paint obtained in Preparation Example 1 was obtained by gravure printing.
To a dry film thickness of 25 μm.
It dried at 30 degreeC for 30 minutes, and obtained the adhesive sheet. Examples 2 to 7 and Comparative Examples 1 to 5 In Example 1, the clear paint was used as shown in Table 2.
Each adhesive sheet was prepared in the same manner as in Example 1 except that
Got. Example 8 Adhesive plastic film (vinyl chloride 50μm,
(Purple adhesive 10 μm)
G-80,202 ”(Kansai Paint Co., Ltd., acrylic urethane
Dry film by electrostatic spray
Paint to a thickness of 25 μm, leave for 10 minutes,
Gravure printing of the clear paint obtained in Preparation Example 1
Paint to a dry film thickness of 25 μm, then 80 ° C
For 30 minutes to obtain an adhesive sheet. [0069]performance test The adhesive sheet obtained as described above was subjected to the following performance test.
Was. Table 2 shows the results. (* 1) Hydrophilicity (outdoor exposure test):
Luminium alloy surface treated plate (0.8 × 150 × 100m
m) to make a test plate, Kansai Paint Co., Ltd.
Tokyo office, set up the test plate at an angle of 30 degrees on the south side,
An external exposure test was performed. Initial and final coating surface of the test plate
The static contact angle with water three months after external exposure was measured using a contact angle
(CAS-150, manufactured by Wa Interface Science Co., Ltd.). (* 2) Stain resistance: The film surface after 3 months of outdoor exposure
Lightness difference from the initial coated plate not exposed
(Lightness difference ΔL * value) was examined. (* 3) Weather resistance (accelerated weather test): above
(* 1) Sunshine weather ome
Gloss retention of coating film after 3000 hours test
(%) Was determined. (* 4) Bending resistance: Test plate created in (* 1) above
Was bent to evaluate the occurrence of cracks.
No crack, ×: cracks). (* 5) Sealant adhesion: on the coating surface of each PSA sheet
Penguin seal SS-1 primer (Sunstar Giken
Co., Ltd.) and penguin seal 7000
(Sunstar Giken Co., Ltd., sealing agent)
Each test plate was prepared by punching and curing at 23 ° C. for 7 days.
For each of these test plates, the primary density was determined by the hand peel method.
After evaluating the adhesion and further immersing in 50 ° C. warm water for 7 days,
Take out and leave at 23 ° C for 2 hours, then use the hand peel method
The secondary adhesion was evaluated (（: no abnormality, Δ: partial peeling,
X: Interfacial separation between the top coat and the primer). (* 6) Sheet adhesiveness: 5 for each adhesive sheet
After immersion in 0 ° C warm water for 7 days, take out and remove at 23 ° C for 2 days.
After standing for a time, the secondary adhesion was evaluated (評 価: no abnormality,
Δ: Partial peeling, ×: Complete peeling). (* 7) Lamination suitability: each adhesive sheet is made of aluminum
Paste on alloy surface treated plate (0.8 × 150 × 100mm)
Adhesion, and further adhesion to the clear coating layer surface of each adhesive sheet
Plastic film (vinyl chloride 50μm, acrylic
A test plate was prepared by applying a 10 μm adhesive).
And slit it to a width of 10 mm.
B type "(manufactured by Shimadzu Corporation, trade name)
Is peeling test at 300mm / min at measuring temperature of 20 ℃ and 5 ℃
And adhesive strength 24 hours after application (N / cm)
Was measured. In addition, "5.9Z" is between 0 and 5.9.
Adhesion is unstable enough to reciprocate the adhesive force without interruption
(Poor lamination suitability). [0072] According to the present invention, self-cleaning of contamination, overlapping
Sheet for architectural exterior walls with excellent adhesiveness and sealant adhesion
Can be obtained. [0073] [Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) B32B 27/28 B32B 27/28 C09D 133/14 C09D 133/14 143/04 143/04 163/00 163 / 00 175/04 175/04 183/00 183/00 201/00 201/00 C09J 201/00 C09J 201/00 E04F 13/00 E04F 13/00 A (72) Inventor Toshiro Nanbu Tsutsujigaoka, Tarumizu-ku, Kobe City, Hyogo Prefecture 7-chome 1722-20 (72) Inventor Hirotoshi Kawaguchi 4-28-6-403 Nishi-Maiko, Tarumi-ku, Kobe, Hyogo Prefecture (72) Inventor Joh Kawamura 6-14, Maikodai, Tarumi-ku, Kobe, Hyogo F-term ( Reference) 4D075 AE03 AE24 CA12 CA32 CA34 CB06 DA06 DB02 DB04 DB07 DB18 DB31 DB34 DB36 DB38 DB39 DB48 DB50 DB63 DC02 EA07 EA35 EA43 EB10 EB13 EB15 EB16 EB19 EB22 EB32 EB33 EB35 EB36 EB38 EB38 EB39 EB42 EB39 EB42 EB39 EB39 EB42 EB39 EB39 EB42 EB38 R00D BA05 BA10A BA10E EH46E GB07 JK06A JL06 JL10D JL14A JL14B JN00E 4J004 AA04 AA05 AA07 AA08 AA09 AA10 AA11 AA14 AA15 AB01 CA03 CA06 CA08 DA02 DA04 CH01 CH1 CH01 CE08 CC011 CC021 CC08 CC011 CC021 CK031 CR071 DJ001 DL121 GA06 GA09 GA13 GA14 NA05 PB05 4J040 CA011 DA051 DC091 DD071 DF041 DF051 ED001 EF001 EK031 LA07 MA01 NA12

Claims (1)

Claims: 1. A release sheet layer (1), an adhesive layer (2),
In a pressure-sensitive adhesive sheet formed by sequentially laminating a base sheet layer (3), a colored coating layer (4), and a clear coating layer (5) as required, the clear coating layer (5) has a main chain. It consists essentially of a vinyl copolymer chain, and has a general formula (I) at the terminal and / or side chain of the main chain. (Wherein, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and 7 to 12 carbon atoms.
A is a monovalent hydrocarbon group selected from the group consisting of
Having at least one hydrolyzable silyl group bonded to a carbon atom represented by the following formula: and having at least one alcoholic hydroxyl group at the terminal and / or side chain of the main chain. 100 parts by weight of the vinyl copolymer (A) component, general formula (II): (Wherein, R ³ is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, R ⁴ is an alkyl group having 1 to 10 carbon atoms, an aryl group, A monovalent group selected from aralkyl groups, b is 0
Or 1), and 1 to 70 parts by weight of the component (B), 0.01 to 10 parts by weight of the epoxysilane compound (C), and isocyanate as a crosslinking agent. A clear coating composition comprising a binder component comprising a resin composition comprising 1 to 100 parts by weight of a compound (D) component containing two or more groups and 0.01 to 10 parts by weight of an organotin compound (E) component is applied. An adhesive sheet for building exterior walls, characterized in that it is formed.