WO1992013920A1 - Composition de resine durcissable - Google Patents
Composition de resine durcissable Download PDFInfo
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- WO1992013920A1 WO1992013920A1 PCT/JP1992/000103 JP9200103W WO9213920A1 WO 1992013920 A1 WO1992013920 A1 WO 1992013920A1 JP 9200103 W JP9200103 W JP 9200103W WO 9213920 A1 WO9213920 A1 WO 9213920A1
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- WIPO (PCT)
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- group
- glycol
- compound
- silicon compound
- composition according
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/16—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
Definitions
- the present invention relates to a novel curable resin composition.
- curable resin compositions containing an alkoxysilane group and a hydroxyl group as functional group components have been proposed, but none of them have been practically satisfactory.
- a mixture of a copolymer containing monomeric alkoxypropyl realalkoxysilane as a monomer component and a hydroxyl group-containing resin is known, and three alkoxysilanes derived from the monomer are known.
- the storage stability of the mixture is poor because the reactivity between the hydroxyl group and the hydroxyl group is too high, and the system becomes viscous and gel even with a small amount of moisture (moisture in the air, moisture contained in raw materials, etc.).
- An object of the present invention is to provide a novel curable resin composition in which the above-mentioned drawbacks have been eliminated.
- Another object of the present invention is to provide a resin composition which has excellent storage stability, does not cause the system to stick or gel even with a small amount of water, and has excellent curability. It is in.
- the present invention has the general formula
- Ri is an organic group having at least one C ⁇ monovalent hydrocarbon group, one R ′ — 0—R ′ group, one R ′ — OO C—R ′ group, or an epoxy group.
- R 2 is the same or different and represents a hydroxyl group or a hydrolyzable group, wherein R ′ is a C ⁇ g divalent hydrocarbon group, and R ′ is a monovalent hydrocarbon group of The general formula obtained by reacting the silicon compound represented by
- the inventor of the present invention has conducted intensive studies to solve the above-mentioned drawbacks of the conventional curable resin composition, and as a result, has been found that a modified silicone having the above-mentioned specific structure is obtained by reacting the above-mentioned specific silicide compound with a glycol component. It has been found that a resin composition obtained by mixing a silicide compound and a hydroxyl group-containing resin satisfies the above object. The present invention has been completed based on such new knowledge.
- the silicon compound as a raw material of the glycol-modified silicon compound (I) used in the composition of the present invention has a general formula
- R 2 represents The same or different, represents a hydroxyl group or a hydrolyzable group, where is a compound represented by (: represents a divalent hydrocarbon group of, and R ′ represents a monovalent hydrocarbon group of). It is.
- examples of the monovalent hydrocarbon group of C in Ri include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group.
- the “alkyl group” may be of any type, linear or branched, such as methyl, ethyl, ⁇ -propyl, isoprovir, n-butyl, isobutyl, sec-butyl, tert-butyl, n-bentyl, isopentinole, tert-benthinole, neoventil, n-hexinole, isohexyl, 1-methylpentyl, 2-methylpentyl, n-heptinole, 5-methylhexyl, n, octyl, Examples include n-nonyl, n-decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, and o
- cyclopropyl group for example, cyclopropyl, cyclobutynole, cyclopentyl, cyclohexyl group, etc., and a cyclohexyl group is particularly preferable.
- the “aryl group” may be any of monocyclic and polycyclic, and includes, for example, phenyl, tolyl, xylyl, naphthyl and the like.
- the “aralkyl group” is an alkyl group substituted with the above aryl group, and examples thereof include a benzyl group and a phenethyl group.
- one R′-0-R ′ group or one R′—OOC—R ′ in the R ′ group is a C ⁇ g divalent hydrocarbon group, preferably A linear or branched alkylene group, for example, a group of methylene, ethylene, propylene, butylene, pentylene, octylene and the like; and is a monovalent hydrocarbon group of C.
- the group is included in the monovalent hydrocarbon group of the above-mentioned C 2 () , but is preferably an “aryl group”.
- R is an organic group having at least one epoxy group
- the curability of the obtained resin composition is further improved.
- the organic group having an epoxy group include a monovalent group in which an aliphatic or alicyclic epoxy group is bonded to a hydrocarbon group or a hydrocarbon group substituted with an acid chain. Organic group.
- the hydrocarbon group is the same divalent hydrocarbon group, preferably a linear or branched alkylene group, for example, methylene, ethylene, propylene, butylene, pentylene,
- a hydrocarbon group substituted with an acid rope is a group in which a part of the divalent hydrocarbon cable group of C is S-substituted with oxygen, for example, -R 3- 0 - R 3 one group, one COO- R single one group (wherein, R 3 represent the same or different C ⁇ divalent charcoal hydrocarbon group.) include groups such as.
- aliphatic or alicyclic epoxy group for example,
- the organic group having an epoxy group in the general formula (1) is preferably the following general formula: One a
- R 4 represents a hydrogen atom or a methyl group
- R 3 is
- the hydrolyzable group of R 2 is a group that forms a hydroxysilane group by hydrolysis, for example, an alkoxyl group of C; a phenoxy group, Liloki
- Aryloxy groups such as methoxy, phenoxy, lamethoxyphenoxy, lantrophenoxy, benzyloxy; acetoxy, propionyloxy, butanoyloxy, benzoyloxy, phenylacytoxy, holmy Ashirokishi groups such as Le Okishi group, and formula one 0 ⁇ c n H ⁇ - ⁇ -R 5 (wherein, R 5 is identical or different alkyl group of C 8, a cycloalkyl group, Ariru group or ⁇ La alkyl N represents an integer of 1 to 3 and m represents 1 to 4 Indicates an integer. ).
- the “0 ⁇ 6 alkoxyl group” may be any of a straight-chain or branched-chain type, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butyroxy, Isobutyroxy, sec-butyroxy, tert-butyroxy, n-pentyl-pentoxy, iso-pentyl-pentoxy, tert-pentyl-pentoxy, neopentyl-t-xy, ⁇ -hexyloxy, isohexyloxy, 1-methylpentyloxy, 2-methylbentyloxy, etc. Is mentioned.
- R 2 has a C 3 alkoxyl group such as methoxy, ethoxy, or n-propoxy group since a resin composition having excellent curability can be obtained.
- the organic group having the compound include 7-glycidoxyprobitritrimethoxysilane, argioxydoxyprobitritriethoxysilane, 2 o Mechirudari shea Dokishipurobiruto Increment Tokishishira emissions, 5 one glycidyl Dokishibuchiruto Rie Tokishishiran aliphatic E Bokishi group containing sila down compounds such, beta - (3, 4-Epokishishi black hexyl) alicyclic such Echiruto re main Tokishishira down Epoxy group-containing silane compounds are preferred.
- glycol component used in the glycol-modified silica compound (I) can be used without any particular limitation as long as it has two hydroxyl groups in one molecule, but is preferably, for example, Diols, polyether diols, dioxy acids, polyester diols, polybutadiene diols and the like.
- the above-mentioned diol has the general formula C p H 2p (OH) 2
- the compound may be of a linear or branched type.
- the polyetherdiol the general formula H ⁇ one C n H 2 q — ⁇ -0 ⁇ (wherein, Q represents an integer
- dioxy acid examples include dimethylolpropionic acid.
- Polyester diols include a dibasic acid (eg, adibic acid, azelaic acid, sebacic acid, dodecane diacid, phthalic acid, etc.) and the above glycol so that two hydroxyl groups remain in one molecule. Polyester diols and lactones obtained by the condensation reaction of
- a tri- or higher valent polyol component other than the above-mentioned glycol component can be appropriately used according to required performance.
- the polyol component include: Trimethylolethane, trimethylolproha. Triol compounds such as glycerin, glycerin, and tris (2-hydroxyxetyl) isocyanurate; 1 mol of the triol compound and an alkylene oxide (eg, ethylene oxide propylene oxide, butylene oxide) etc.) by reacting a 1 3 mol Porieteruto triol; upper Quito triol compounds 1 mol diol 1 represented by the dibasic acid 1 3 moles ⁇ beauty formula C p H 2p (OH) 2
- a trivalent polyol component such as polyestertriol or a tetraol compound such as pentaerythritol, which is obtained by reacting 3 moles of the compound; ether tetraol; ⁇ Te Toraoru compound 1 mol
- the tri- or higher valent polyol component may be blended in an amount of about 50% by weight or less, preferably about 0 to 30% by weight in total with the glycol component.
- the glycol component and the trivalent or higher valent polyol component have a molecular weight of about 62 to 3000, preferably about 62 to 500.
- the reaction with the silicon compound, the glycol component and the optionally used trivalent or higher polyol component is carried out by heating a mixture of these components, preferably in the presence of a catalyst, to carry out a dehydration or dealcoholization reaction.
- a catalyst preferably a catalyst
- the carboxyl group can be used as an internal catalyst.
- the mixing ratio of the silicon compound and the glycol component is preferably about 1 to 0.5 mole, preferably 1 to 0.5 mole, of the glycol component and, if necessary, the trivalent or higher polyvalent component per mole of the silicon compound. Is preferably in the range of about 0.98 to 0.7 mole. If the mixing ratio of the glycol component and the trivalent or higher polyvalent component is more than about 1 mol, the curability is inferior.On the other hand, if the mixing ratio is less than about 0.5 mol, a large amount of free alkoxysilane remains and the storage is stable. It is not preferable because the properties may decrease.
- the catalyst used in the reaction with the silicon compound, the glycol component and the trivalent or higher polyvalent component includes, for example, a metal alkoxide, a metal chelate compound and an acidic compound.
- Alkoxides include, for example, aluminum trimethoxide, aluminum trietoxide, aluminum tripropoxide, aluminum trioxide.
- Aluminum alkoxides such as butoxide; Titanium methoxide tramethoxide, Titanium tetraethoxyt Titanium tetrapropoxide, Titanium tetrabutoxide and other titanium alkoxides; Zirconium tetramethoxide, Zirconium tetraethoxide And zirconium alkoxides such as zirconium tetrapropoxide and zirconium tetrabutoxide.
- Suitable metal chelate compounds include, for example, the above metal alkoxides; and 3-diketones.
- reactants with chelating agents such as esters having a hydroxyl group at the yS position (eg, salicyl aldehyde) and esters having a hydroxyl group at the yS position (methyl salicylate), and acidic compounds include, for example, methanesulfonic acid, ethanesulfonic acid, and benzenesulfonic acid.
- p-organic protonic acids such as toluenesulfonic acid; and inorganic protonic acids such as phosphoric acid, phosphonic acid, sulfuric acid, and hydrochloric acid.
- the mixing ratio of the above catalyst is 100 parts by weight based on the total weight of the silicon compound, the glycol component, and the trivalent or higher valent polyol component.
- the range is preferably about 0.001 to 10 parts by weight, more preferably about 0.05 to 1 part by weight.
- the heating conditions in the above reaction can be generally carried out at a temperature of about 80 to 250 hours for about 1 to 10 hours.
- glycol-modified silicon compound (I) has the general formula 1
- a in the above unit formula (2) represents a residue of a dalicol component, and two hydroxyl groups of the glycol component react with a silica compound to form a divalent group having no hydroxyl group.
- a diol include one C p H 2p — group
- those using a polyether diol include — C n H 2q —— E- 0 - such as C q H 2 q ⁇ "7Ty group as a typical example.
- Each of the structural units of the formulas (2) and (3) may be repeated in a block shape or a random shape.
- the molecular terminal of the glycol-modified silicide compound (I) is derived from a hydroxyl group and Z or a hydrolyzable group directly bonded to a silicon atom derived from the silicide compound, glycol, or a trivalent or higher valent polyol component. It can have a hydroxyl group or the like.
- the glycol-modified silicon compound (I) contains the structural unit represented by the general formula (2) in the compound (I) in an amount of about 50 to 100% by weight, preferably about 80 to 99% by weight. Those included in the box are desirable. It is desirable that the compound (I) contains an average of about 2 to 50, preferably an average of about 5 to 30, one Sir group per molecule. New One S i the number of R 2 groups is decreased curability below about 2 ⁇ , conversely, storage stability greater than an average of about 50 to no properly preferred because it tends to decrease.
- the number of epoxy groups in the compound (I) is an average in one molecule.
- About 0.1 to 50, preferably 0.5 to 30 on average is desirable from the viewpoint of improving curability and preventing a decrease in storage stability.
- the glycol modified silicide (I) can have a molecular weight of about 500 to 50,000, preferably about 1,000 to 5,000. If the molecular weight is less than about 500, the performance of the cured product is not sufficient. On the other hand, if the molecular weight is more than about 50,000, the solubility in an organic solvent and the like decrease, which is not preferable.
- the resin (II) used in the composition of the present invention can be appropriately selected from conventional ones without any particular limitation as long as it contains two or more hydroxyl groups in one molecule on average.
- the resin include a hydroxyl group-containing polymerizable unsaturated monomer (for example, hydroxy (cyclo) alkyl (meth) acrylate, hydroxy (cyclo) alkyl vinyl ether, Nyl alcohol, alkylene glycol mono (meta) Acrylates and adducts of these with lactones) and, if necessary, other polymerizable unsaturated monomers (for example, (cyclo) alkyl (meta) acrylates , Vinyl aromatic compounds, (meth) acrylonitrile, vinyl ether, aryl ether, vinyl ester, propyl ester, olefin compounds, (meta) acrylic acid, etc.
- a fluorine-containing polymer contained as a component a polybasic acid (for example, a tribasic or tetrabasic acid such as the dibasic acid, (anhydrous) trimellitic acid, pyromellitic acid, etc.) and a polyhydric alcohol (For example, the above-mentioned diols, tri- or higher valent polyols) and, if necessary, monobasic acids (for example, fatty acids, benzoic acids and derivatives thereof) as polyester resins obtained from vinyl acetate; Resins and other modified resins obtained by partially or wholly hydrolyzing a polymer containing as a body component (for example, an epoxy obtained by reacting a carboxyl group-containing resin with an epoxy resin) RESIN
- the resin ( ⁇ ) can generally have a molecular weight in the range of about 500 to 100,000, preferably about 1,000 to 50,000. If the molecular weight is less than about 500, the performance of the cured product will decrease. Conversely, if the molecular weight is greater than about 100,000, the solubility in organic solvents and the like will decrease, which is not preferred.
- the curable resin composition of the present invention can be obtained by mixing the compound (I) and the resin ( ⁇ ).
- the mixing ratio of the two is the total weight (solid content) of the compound (I) and the resin ( ⁇ ), 1-99% by weight, preferably 10-90% by weight,
- the composition has excellent storage stability and cured film performance. It is not very good because it is difficult to obtain o
- the resin composition of the present invention can contain a carboxyl group in the compound (I) and the compound (I).
- the carboxyl group has the advantage that the low-temperature curability is excellent.
- the resin composition of the present invention includes, for example, a curing catalyst such as the above-mentioned metal alcohol, a metal chelate compound, and an acidic compound. , which improves the low-temperature curability.
- the compounding amount of the curing catalyst is suitably about 0.001 to 10 parts by weight based on 100 parts by weight of the total of the above-mentioned compound (I) and resin ( ⁇ ). It is.
- the curable resin composition of the present invention can contain an organic solvent, an inorganic pigment, an organic pigment, a dye, a fluidity modifier, an ultraviolet absorber, and a light stabilizer, if necessary.
- the curable resin composition of the present invention can be used as a resin component for paints, adhesives, printing inks and the like.
- the method of curing the resin composition of the present invention can be suitably carried out by applying a liquid in which the above resin composition is usually dissolved or dispersed in an organic solvent to a base material, and then drying.
- the organic solvent can be used without any particular limitation as long as it can dissolve or stably disperse the compound (I) and the resin (II).
- an aromatic organic solvent for example, Benzene, toluene, etc.
- ketone-based organic solvents eg, aceton, methylethylketone, methylisobutylketone, etc.
- ester-based organic solvents eg, ethyl acetate, butyl acetate, etc.
- ethers Organic solvents (eg, hexyl ether), cellosolve organic solvents (eg, ethyl ethyl solvent, ethyl solvent, propylene glycol monomethyl ether, etc.), carbitol organic solvents (eg, For example, methyl carbitol, butyl carbitol, etc., organic solvents such as glycol (eg, ethylene glycol dimethyl ether), organic solvents such as diglyme (eg, ethylene glycol dimethyl ether), cello sorbate ⁇ organic solvents (eg, ethylene glycol) Coal monoacetate, methyl
- the base material may be, for example, aluminum, iron, net, tin, stainless steel, submarine, or an alloy or plating thereof, or a metal, a plastic, or a glass whose surface is subjected to a chemical conversion treatment. And wood, concrete, and coated products obtained by applying a coating to these.
- the coating is dry film thickness, usually about l ⁇ n! ⁇ 100 ⁇ m, preferably about 5 ⁇ ⁇ m ⁇ 80m.
- Curing is usually performed by heating at a temperature of about 120 to 180 minutes for about 30 to 60 minutes, and as a cured resin composition, the compound (I) and / or The resin ( ⁇ ) containing a carboxyl group or the composition containing a curing catalyst It is carried out by heating at a temperature of about 80 to 180 for about 10 to 60 minutes.
- the reaction between a functional group derived from the unit formula (2) (a hydroxyl group directly bonded to silicon, a hydrolyzable group, an epoxy group, etc.) and a hydroxyl group does not progress at all near room temperature.
- a functional group derived from the unit formula (2) a hydroxyl group directly bonded to silicon, a hydrolyzable group, an epoxy group, etc.
- a mixture of 1 mol of methyl triethoxysilane, 0.93 mol of ethylene glycol and IOOOPPm of aluminum trisacetylacetonate IOOOPPm was heated from 80 to 150 over 3 hours, and deethanolized. The reaction was performed to obtain a silicon compound ( ⁇ ).
- the obtained silicon compound ( ⁇ ) has a molecular weight of 2000, a Gardner viscosity ST, and a formula
- the temperature was raised to carry out a methanol removal reaction to obtain a silicon compound (iii).
- the obtained silicon compound (Hi) has a molecular weight of 12,000, a gaseous donor viscosity P, and a formula
- A represents the residue of the above-mentioned polyester diol.
- the number of methoxysilane groups in a molecule was about 28 on average.
- Production Example 4 Production of silicon compound (iV) 1 mol of finynyl trimethoxysilane and 0.94 mol of dimethylolpropionic acid were heated from 80 to 150 over 3 hours, followed by demethanol reaction. A silica compound (iv) was obtained. The obtained silicon compound (iV) has a molecular weight of 5,000, a Gardner viscosity Z 3 ,
- the compound had a unit structure represented by 0 C H 3 C 00 H, and the number of methoxysilane groups in the molecule was about 18 C on average.
- Each ethoxysilane group has one molecular structure represented by the following formula:
- the average was about 10 in o.
- the temperature was raised and a methanol removal reaction was performed to obtain a silicon compound (Vi).
- the obtained silicon compound (vi) has a molecular weight of 3800, a Gardner viscosity V, and a formula
- silicide (vii) has a molecular weight of 3800, a Gardner viscosity W, and a formula
- the average was about 15 per molecule.
- a reaction vessel 20 parts of trimethylolpropane, 30 parts of neopentyl glycol and 50 parts of phthalic anhydride are mixed, and after an esterification reaction is performed at 200 to 250 ° C, xylene is mixed and solidified.
- a resin (ii) solution having a concentration of 50% was obtained.
- the resin (ii) had a (town fat) molecular weight of 4000 and a Gardner viscosity (solid content of 50%) T.
- compositions of Examples 1 to 11 were obtained with the formulations shown in Table 1.
- the results of the storage stability, gel fraction (curability), adhesion and acid resistance of the compositions are shown in Table 1. .
- Compound amount 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
- the hydroxyl group-containing resin ( ⁇ ) solution is Lumiflon LF-911-8 (Asahi Glass Co., Ltd. product, molecular weight 1500, hydroxyl value 130, fluorine-containing resin) 50% solution of xylene in water
- catalyst (i) is aluminum tris-acetyl acetate
- catalyst (ii) is para-toluenesulfonic acid.
- Table 1 shows storage stability, gel fraction and performance. Was carried out under the following conditions.
- Gel fraction The compositions of Examples and Comparative Examples were applied to a tin plate with a dry film thickness of 30 and heated under the baking conditions shown in Table 1 to obtain a cured film. Next, the cured film was peeled off from the plate with mercury, and the film was extracted for 18 hours at a dry distillation temperature of an acetone solvent. The calculation of the gel fraction is
- Film appearance Abnormalities in film appearance such as blemishes and reduced gloss were visually observed.
- Adhesion The compositions of Examples and Comparative Examples were applied to a zinc phosphate-treated copper plate so that the dry film thickness was 30 m, and then heated under the baking conditions shown in Table 1 as a material used. Create 100 goban eyes that reach the substrate at 1 mm intervals on the membrane surface, attach a cellophane tape on it, press down evenly with a uniform force, and then quickly peel off the tape. The remaining number of Goban eyes was counted.
- Acid resistance The sample is the same as that used for the above adhesion Was used. After placing a 60% sulfuric acid (40 te) on the film surface: a spot test was performed for 3 hours, abnormalities of the film such as a decrease in blister gloss on the film surface were observed.
- silicide compound of the general formula (I) contains an organic group having at least one evoxy group as 1 ⁇
- silicide compound (Vti) has a molecular weight (5 beak molecules measured by gel permeation chromatography, hereinafter the same meaning) 2500, Gardner viscosity W, formula
- Production Example 1 1 Production of silicon compound (be)
- the obtained silicon compound (X) has a molecular weight of 5,000, Gardona monoviscosity Z 3,
- the average number of methoxysilane groups was about 22 in one molecule, and the number of epoxy groups was about 10 in one molecule.
- silicide compound (X i) has a molecular weight of 400
- A represents the residue of the above-mentioned polyester diol.
- the methoxysilane group has an average of about 12 per molecule, and the epoxy group has an average of about 12 epoxy groups per molecule. The average was about eight.
- A represents the residue of the above-mentioned polyester diol.
- the number of ethoxyquinsilane groups in the molecule is about 7 and the number of epoxy groups is about 7 in the molecule. 1. There were five.
- Production Example 15 Production of Silicon Compound (Xiii) 7 — A mixture of 0.5 mol of glycidoxypropyl trimethoxysilane, 0.5 mol of funinyl triethoxysilane, 0.9 mol of styrene glycol and 500 ppm of aluminum tris-acetylacetonate from 80 The temperature was raised to 150 over 3 hours, and a demethanol reaction was carried out to obtain a silicon compound (xiii). The obtained silicon compound (X iii) has a molecular weight of 2600, a Gardner viscosity U, and a formula
- the average number of methoxysilane groups was about 12 per molecule, and the average number of epoxy groups was about 5 per molecule.
- the temperature was raised and a methanol removal reaction was performed to obtain a silicon compound (XiV).
- the obtained silicon compound (X iV) has a molecular weight of 800, a Gardner viscosity N, and a formula
- A represents the residue of the above polyester diol.
- the number of methoxysilane groups is about 22 in one molecule and the average number of epoxy groups is about 2 in one molecule. It was an individual.
- compositions of Examples 12 to 23 were obtained with the formulations shown in Table 2. Storage stability of the composition, gel fraction (curability), adhesion The results of resistance and acid resistance are shown in Table 2,
- the hydroxyl group-containing resin (W) solution is Lumiflon LF-911 (product of Asahi Glass Co., Ltd., molecular weight 1500, hydroxyl value 130, fluorine-containing resin). ), 50% xylene solution, catalyst (i) represents aluminum tris-acetyl acetate, catalyst (ii) represents para-toluenesulfonate.
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Description
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Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP3/100619 | 1991-02-04 | ||
JP10061991A JPH04253770A (ja) | 1991-02-04 | 1991-02-04 | 硬化性樹脂組成物及びその硬化方法 |
JP3/37375 | 1991-03-04 | ||
JP3737591A JPH04275320A (ja) | 1991-03-04 | 1991-03-04 | 硬化性樹脂組成物及びその硬化方法 |
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WO1992013920A1 true WO1992013920A1 (fr) | 1992-08-20 |
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PCT/JP1992/000103 WO1992013920A1 (fr) | 1991-02-04 | 1992-02-04 | Composition de resine durcissable |
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EP (1) | EP0523242A4 (ja) |
CA (1) | CA2079481A1 (ja) |
WO (1) | WO1992013920A1 (ja) |
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JPS5974149A (ja) * | 1982-10-20 | 1984-04-26 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
JPS6031556A (ja) * | 1983-07-29 | 1985-02-18 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB766627A (en) * | 1954-05-24 | 1957-01-23 | Midland Silicones Ltd | Synthetic resinous compositions |
JPS5712058A (en) * | 1980-06-25 | 1982-01-21 | Dainippon Ink & Chem Inc | Curable resin composition |
US4413086A (en) * | 1982-03-04 | 1983-11-01 | Ppg Industries, Inc. | Coating compositions containing organosilane-polyol |
JPS58168625A (ja) * | 1982-03-31 | 1983-10-05 | Dainippon Ink & Chem Inc | アルコキシシラン変性樹脂の製造方法 |
JPS60212453A (ja) * | 1984-04-09 | 1985-10-24 | Kanegafuchi Chem Ind Co Ltd | 硬化性樹脂組成物 |
JP2559597B2 (ja) * | 1987-09-08 | 1996-12-04 | 関西ペイント株式会社 | 生物付着防止方法 |
EP0419669B1 (en) * | 1989-02-10 | 1997-07-09 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Thermosetting composition |
-
1992
- 1992-02-04 WO PCT/JP1992/000103 patent/WO1992013920A1/ja not_active Application Discontinuation
- 1992-02-04 CA CA 2079481 patent/CA2079481A1/en not_active Abandoned
- 1992-02-04 EP EP19920904232 patent/EP0523242A4/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5974149A (ja) * | 1982-10-20 | 1984-04-26 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
JPS6031556A (ja) * | 1983-07-29 | 1985-02-18 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP0523242A4 * |
Also Published As
Publication number | Publication date |
---|---|
EP0523242A1 (en) | 1993-01-20 |
CA2079481A1 (en) | 1992-08-05 |
EP0523242A4 (en) | 1993-07-28 |
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