JP5707526B2 - Primer composition - Google Patents

Description

  The present invention relates to an organic polymer having a silicon-containing group (hereinafter also referred to as “reactive silicon group”) having a hydroxy group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. The present invention relates to a primer composition containing The present invention is suitable as a primer composition, and relates to a technique for improving the adhesion and moisture resistance between various adherends and an adhesive layer.

  An organic polymer containing at least one reactive silicon group in the molecule is crosslinked at room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture, etc. It is known to have the property of being obtained.

  Among these polymers having a reactive silicon group, polyoxyalkylene polymers and polyisobutylene polymers having a main chain skeleton are disclosed in (Patent Document 1), (Patent Document 2), etc. Already industrially produced, it is widely used for applications such as sealing materials, adhesives and paints. Although these sealing materials and adhesives generally adhere to various base materials, there is a problem that they are difficult to adhere to olefin base materials, concrete in which water is immersed, and the like. Although the technique which improves the water-resistant adhesiveness with respect to a porous base material by using a special amino group containing silane coupling agent is illustrated by (patent document 3), the effect was inadequate.

  On the other hand, when used for a base material that is difficult to adhere, a primer is generally used in order to enhance adhesion. However, as disclosed in (Patent Document 4), the primer generally contains a solvent.

JP-A-52-73998 JP-A 63-6041 JP-A-6-299062 JP 2009-126923 A

  A curable composition containing an organic polymer having a reactive silicon group as a main component is also used as an adhesive for wooden floors. However, there is a case where the adhesion with the concrete base is bad, and there is a problem that the flooring floats especially when the floor is cleaned with water. This problem is caused by poor adhesion between the adhesive and the concrete base when water is applied. In such a case, it is a common practice to apply a primer on the base substrate to improve the adhesion with the adhesive. However, most of the primers used in the past contain a highly volatile solvent, which is problematic in terms of safety to the human body. In particular, when used for a wooden floor in a room, since it gradually evaporates even after construction, it is exposed to the human body for a long period of time, and a highly safe material has been demanded.

In order to solve these problems, the present inventors have conducted extensive studies and found that in addition to an organic polymer having a reactive silicon group, heavy calcium carbonate, and aminosilane, a silane having a urethane group and / or a urea group. It has been found that by using a coupling agent and / or a silane coupling agent having an alkyl group having 8 or more carbon atoms as a primer, adhesion of a wood flooring adhesive to a concrete base is improved. . It was also discovered that when the above composition is cured in a thin film, the water vapor transmission rate is low. The fact that water vapor hardly permeates is considered to contribute to not lowering the adhesiveness even when water is applied to the concrete part, and the present invention has been completed.
That is, the present invention
1). (A) an organic polymer having a silicon group that can be crosslinked by forming a siloxane bond, (B) heavy calcium carbonate, (C) a silane coupling agent having an amino group, (D) a urethane group and / or a urea. The primer composition containing the silane coupling agent which has group.
2). (A) an organic polymer having a silicon group that can be crosslinked by forming a siloxane bond, (B) heavy calcium carbonate, (C) a silane coupling agent having an amino group, (E) having 8 or more carbon atoms The present invention relates to a primer composition comprising a silane coupling agent having a long-chain alkyl group.
3). The present invention relates to a primer composition in which the main chain skeleton of the organic polymer (A) is a polyoxyalkylene polymer and / or a (meth) acrylic acid ester polymer.
4). The present invention relates to a primer composition in which the content of a dibutyltin compound contained in the curable composition is 0.3% by weight or less.
5). The curing catalyst contained in a curable composition is related with the primer composition which is a dioctyl tin compound.
6). The present invention relates to a primer composition in which the content of a plasticizer contained in the curable composition is 15% by weight or less.
7). The present invention relates to a primer composition applied to a concrete base.
8). The present invention relates to a primer composition used between a concrete substrate and a floor adhesive.

  The present invention provides a primer composition used for an adhesive for floors, which has good adhesiveness to the ground concrete and does not contain an organic solvent and is friendly to the human body and the environment.

It is the figure which showed the measuring method of the water vapor amount which permeate | transmitted the thin layer based on Example 1 and Example 2 of this invention.

  The present invention will be described in detail below.

  The primer composition of the present invention contains an organic polymer (A) having a reactive silicon group as an essential component. The organic polymer (A) has at least one reactive silicon group on average per molecule. Here, the reactive silicon group is an organic group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom.

  The organic polymer (A) having a reactive silicon group has a characteristic that a siloxane bond is formed by a reaction accelerated by a silanol condensation curing catalyst and is crosslinked.

As the reactive silicon group, the general formula (1):
-SiR ¹ _3-a X _a (1)
((3-a) pieces of R ¹ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and —OSi (R ') ³ (R' is each independently a hydrocarbon group having 1 to 20 carbon atoms.) And is at least one selected from the group consisting of triorganosiloxy groups. Each independently represents either a hydroxyl group or a hydrolyzable group, and a is an integer of 1 to 3).

  The hydrolyzable group represented by X in the general formula (1) is not particularly limited, and examples thereof include known hydrolyzable groups such as a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, and a ketoximate. Group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group and the like. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. preferable.

  A hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and when two or more hydrolyzable groups or hydroxyl groups are bonded to a silicon atom in a reactive silicon group. They may be the same or different.

In addition, R ¹ described in the general formula (1) is not particularly limited, and examples thereof include alkyl groups such as a methyl group and an ethyl group, cycloalkyl groups such as a cyclohexyl group, aryl groups such as a phenyl group, and benzyl groups. An aralkyl group such as is exemplified, and among these, a methyl group is preferable.

  The reactive silicon group described in the general formula (1) is not particularly limited, and for example, a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diiso Examples thereof include a propoxymethylsilyl group, a methoxydimethylsilyl group, and an ethoxydimethylsilyl group. Among these, a trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are preferable, and a trimethoxysilyl group is more preferable because of high activity and good curability.

  In addition, a dimethoxymethylsilyl group is particularly preferred from the viewpoint of good curability and storage stability of the primer composition, and the alcohol produced by the hydrolysis reaction of the reactive silicon group is highly safe ethanol. Therefore, a triethoxysilyl group is particularly preferable.

  The method for introducing the reactive silicon group is not particularly limited, and examples thereof include known methods, and examples thereof include the following methods (a) to (c).

  (I). A polymer having a functional group such as a hydroxyl group in the molecule is reacted with an organic compound having an active group and an unsaturated group that are reactive with the functional group to obtain a polymer having an unsaturated group. Alternatively, a polymer having an unsaturated group is obtained by copolymerization with an epoxy compound having an unsaturated group. Next, the reaction product obtained is hydrosilylated by allowing hydrosilane having a reactive silicon group to act.

  (B). A method of reacting a compound having a mercapto group and a reactive silicon group with an organic polymer having an unsaturated group obtained in the same manner as in the method (a).

  (C). A method of reacting an organic polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in a molecule with a compound having a reactive functional group and a reactive silicon group.

  Among these methods, the method (a) or the method (c) in which the polymer having a hydroxyl group at the terminal is reacted with the compound having an isocyanate group and a reactive silicon group has a relatively short reaction time. Is preferable because a high conversion can be obtained. Moreover, the primer composition which has as a main component the organic polymer which has the reactive silicon group obtained by the method (a) is the primer composition which has the organic polymer obtained by the method (c) as a main component. As a result, a primer composition with good workability can be obtained, and the organic polymer obtained by the method (b) was obtained by the method (a). Since the odor based on mercaptosilane is stronger than that of the organic polymer, the method (A) is more preferable.

  The hydrosilane compound used in the method (a) is not particularly limited. For example, halogenated hydrosilanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyl Alkoxysilanes such as diethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane; methyldiacetoxysilane, phenyl And acyloxyhydrosilanes such as diacetoxysilane; ketoximate hydrosilanes such as bis (dimethylketoxymate) methylsilane and bis (cyclohexylketoximate) methylsilane. Among these, halogenated hydrosilanes and alkoxyhydrosilanes are preferable, and the primer composition mainly composed of the obtained organic polymer (A) has a mild hydrolyzability and is easy to handle. preferable. Among the above-mentioned alkoxyhydrosilanes, it is easy to obtain, and the properties of the primer composition and the cured product mainly composed of the obtained organic polymer (A) (curability, storage stability, elongation property, tensile strength, etc.) Is preferable, methyldimethoxysilane is preferable.

  The method for synthesizing (b) is not particularly limited. For example, a compound having a mercapto group and a reactive silicon group is converted into an organic polymer by a radical addition reaction in the presence of a radical initiator and / or a radical source. Examples thereof include a method for introducing into an unsaturated binding site. The compound having a mercapto group and a reactive silicon group is not particularly limited. For example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldi Examples include ethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane.

  The method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group in the synthesis method of (c) is not particularly limited, and is disclosed in, for example, JP-A-3-47825. The method that is done. The compound having an isocyanate group and a reactive silicon group is not particularly limited. For example, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldi Examples include ethoxysilane, isocyanate methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, and isocyanatemethyldiethoxymethylsilane.

  A silane compound in which three hydrolyzable groups are bonded to one silicon atom, such as trimethoxysilane, may cause a disproportionation reaction to proceed rapidly. As the disproportionation reaction proceeds, dangerous compounds such as dimethoxysilane are formed.

  However, such disproportionation reaction does not proceed with γ-mercaptopropyltrimethoxysilane or γ-isocyanatopropyltrimethoxysilane. For this reason, when using a group in which three hydrolyzable groups are bonded to one silicon atom, such as a trimethoxysilyl group, it is preferable to use the synthesis method (b) or (c). .

On the other hand, general formula (2):
H- (SiR ² ₂ O) _n SiR ² ₂ -R ³ -SiX ₃ (2)
(Three X's are the same as in the general formula (1). (2n + 2) R ^{2 s} are each independently a hydrocarbon group. R ³ is a divalent organic group. In the silane compound represented by (19), the disproportionation reaction does not proceed. Therefore, when a group in which three hydrolyzable groups are bonded to one silicon atom is introduced by the synthesis method (a), a silane compound represented by the general formula (2) may be used. preferable.

R ² in the general formula (2) is not particularly limited as long as it is a hydrocarbon group, and among these, a hydrocarbon group having 1 to 20 carbon atoms is preferable from the viewpoint of availability and cost. A hydrocarbon group having 1 to 8 carbon atoms is more preferable, and a hydrocarbon group having 1 to 4 carbon atoms is particularly preferable.

R ³ in the general formula (2) is not particularly limited as long as it is a divalent organic group, and among these, from the viewpoint of availability and cost, a divalent carbon atom having 1 to 12 carbon atoms. A hydrogen group is preferable, a divalent hydrocarbon group having 2 to 8 carbon atoms is more preferable, and a divalent hydrocarbon group having 2 carbon atoms is particularly preferable.

  N described in the general formula (2) is an integer of 0 to 19, and among these, 1 is preferable from the viewpoint of availability and cost.

  Examples of the silane compound described in the general formula (2) include 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane, 1- [2- (trimethoxysilyl) propyl]. Examples include -1,1,3,3-tetramethyldisiloxane and 1- [2- (trimethoxysilyl) hexyl] -1,1,3,3-tetramethyldisiloxane.

  As the organic polymer (A) having a reactive silicon group, any polymer having a linear or branched structure in the molecule can be used, and the number average molecular weight is measured by GPC. Is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, particularly preferably from 2,000 to 30,000, and most preferably from 2,500 to 20,000. If the number average molecular weight is less than 500, the resulting cured product tends to be inferior in elongation characteristics, and if it exceeds 100,000, the primer composition tends to have high viscosity and tends to be inferior in workability.

  The number of reactive silicon groups contained in one molecule of the organic polymer (A) is preferably 1 or more, and preferably 1.1 to 5 as an average value. When the number of reactive silicon groups contained in the molecule is less than 1 on average, the primer composition tends to be inferior in curability, and the resulting cured product tends to hardly exhibit good rubber elastic behavior. is there.

  The reactive silicon group may be at the end of the main chain, at the end of the side chain, or at both. In particular, when the reactive silicon group is only at the end of the main chain, the effective network length of the organic polymer component contained in the resulting cured product is increased, so that the rubber exhibits high strength, high elongation, and low elastic modulus. It becomes easier to obtain a cured product.

  The main chain skeleton of the organic polymer (A) is preferably composed of one or more selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom.

  The main chain skeleton of the organic polymer (A) is not particularly limited. For example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxy Polyoxyalkylene polymers such as propylene-polyoxybutylene copolymers; ethylene-propylene copolymers, isobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or butadiene and acrylonitrile and / or Or a copolymer with styrene, polybutadiene, isoprene or a copolymer of butadiene with acrylonitrile and styrene, a hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers, etc. Hydrocarbon polymer; polyester polymer obtained by condensation of dibasic acid such as adipic acid and glycol, or ring-opening polymerization of lactones; compounds such as ethyl (meth) acrylate and butyl (meth) acrylate (Meth) acrylic acid ester polymer obtained by radical polymerization; (meth) acrylic acid ester compound, vinyl polymer obtained by radical polymerization of compounds such as vinyl acetate, acrylonitrile and styrene; Polymer obtained by polymerizing vinyl compound with polysulfide; Polysulfide polymer; Polyamide 6 by ring-opening polymerization of ε-caprolactam, Polyamide 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, Hexamethylenediamine and Sebacin Polyamide 6 · 10, ε-aminounde by acid condensation polymerization Polyamide 11 by polycondensation of acid, polyamide 12 by ring-opening polymerization of ε-aminolaurolactam, polyamide-based polymer such as a copolyamide composed of a plurality of the above polyamides; polycarbonate by polycondensation from bisphenol A and carbonyl chloride, etc. Organic polymers such as polycarbonate polymers; diallyl phthalate polymers;

  Among these, the polyoxyalkylene polymer and the organic polymer (A) having a (meth) acrylic acid ester polymer in the main chain skeleton have a relatively low glass transition temperature, and the resulting cured product has a low temperature resistance. It is preferable because it is excellent.

  The glass transition temperature of the organic polymer (A) having a reactive silicon group is not particularly limited, and is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and −20 ° C. or lower. Particularly preferred. When the glass transition temperature exceeds 20 ° C., the viscosity of the primer composition in winter or cold regions tends to be high and workability tends to be poor, and the flexibility of the resulting cured product is lowered, resulting in a decrease in elongation. Tend.

  The glass transition temperature can be determined by DSC measurement according to the measurement method defined in JIS K7121.

  Furthermore, the organic polymer having a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer in the main chain skeleton has high moisture permeability and was used as a main component of a one-pack type adhesive or a sealing material. At this time, the cured product obtained is excellent in deep part curability and has excellent adhesiveness, and an organic polymer having a polyoxyalkylene polymer in the main chain skeleton is most preferable.

The polyoxyalkylene polymer used as the main chain skeleton of the organic polymer (A) has the general formula (3):
-R ⁴ -O- (3)
(R ⁴ is a linear or branched alkylene group having 1 to 14 carbon atoms).

R ⁴ in the general formula (3) is not particularly limited as long as it is a linear or branched alkylene group having 1 to 14 carbon atoms, and among these, a linear chain having 2 to 4 carbon atoms. A branched or branched alkylene group is preferred.

The repeating unit described in the general formula (3) is not particularly limited. For example, —CH ₂ O—, —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH (C _{2 H 5) O -, - CH} 2 C (CH 3) 2 O -, - CH 2 CH 2 CH 2 CH 2 O-
Etc.

  The polyoxyalkylene polymer may be composed of only one type of repeating unit or may be composed of a plurality of types of repeating units. Especially when used for applications such as sealing materials, the organic polymer (A) mainly composed of a propylene oxide polymer as the main chain skeleton is amorphous and has a relatively low viscosity. preferable.

  The production method of the polyoxyalkylene polymer is not particularly limited and includes known methods. For example, a method using an alkali catalyst such as KOH, an organoaluminum compound disclosed in JP-A-61-215623, and Method using transition metal compound-porphyrin complex such as a complex obtained by reacting with porphyrin as a catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US US Pat. No. 3,278,595, US Pat. No. 3,427,256, US Pat. No. 3,427,334, US Pat. No. 3,427,335, and the like, and a polyphosphazene salt disclosed in JP-A-10-273512 , As a catalyst, JP-A-11 A method using a phosphazene compound disclosed in JP 060722 as catalyst.

  The production method of the polyoxyalkylene polymer having a reactive silicon group is not particularly limited, and examples thereof include known methods. For example, JP-B Nos. 45-36319, 46-12154, and JP-A-50-156599 are known. No. 54-6096, No. 55-13767, No. 55-13468, No. 57-164123, No. 3-2450, US Pat. No. 3,362,557, US Pat. No. 4345053, US Pat. No. 4,366,307, US Pat. No. 4,960,844, etc., JP-A 61-197631, JP-A 61-215622, JP-A 61-215623, JP-A 61-218632, JP-A-3-72527, JP-A-3-47825, High molecular weight (number average molecular weight 6,000 or more) molecules disclosed in JP-A-8-231707 And a method of distribution is narrow (Mw / Mn 1.6 or less) polymer is obtained and the like.

  When the polyoxyalkylene polymer having a reactive silicon group is blended in the primer composition, only one type may be blended or a plurality of types may be blended.

  The (meth) acrylic acid ester polymer used as the main chain skeleton of the organic polymer (A) is a polymer comprising a (meth) acrylic acid ester compound as a repeating unit. In addition, the said description method ((meth) acrylic acid ester) represents acrylic acid ester and / or methacrylic acid ester, and also represents the same meaning also in subsequent description methods.

  The (meth) acrylic acid ester compound used as the repeating unit is not particularly limited. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n -Propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, (meth) acrylate n -Hexyl, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate , Dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, Benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic Stearyl acid, glycidyl (meth) acrylate, γ- (methacryloyloxy) propyltrimethoxysilane, γ- (methacryloyloxy) propyldimethoxymethylsilane, ethylene oxide adduct of (meth) acrylic acid, trifluoro (meth) acrylic acid Methylmethyl, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, (meth) acrylic acid Perfluoroethyl, (meth) a Trifluoromethyl laurate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, ( Examples include (meth) acrylic acid compounds such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate.

  The (meth) acrylic acid ester polymer includes a copolymer of a (meth) acrylic acid ester compound and a vinyl compound copolymerizable therewith.

  The vinyl compound is not particularly limited, and for example, styrene compounds such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof; silicon groups such as vinyl trimethoxy silane and vinyl triethoxy silane. Vinyl-based compounds having: maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide , Maleimide compounds such as butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; acrylonitrile, meta Vinyl compounds having a nitrile group such as rilonitrile; Vinyl compounds having an amide group such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; ethylene And alkenes such as propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like. A plurality of these can be used as a copolymerization component.

  Among the (meth) acrylic acid ester-based polymers obtained from the above compounds, an organic polymer having a main chain skeleton of a copolymer composed of a styrene compound and a (meth) acrylic acid compound is obtained. Is preferable from the viewpoint of excellent physical properties, more preferably an organic polymer having a copolymer consisting of an acrylate compound and a methacrylic acid ester compound in the main chain skeleton, and an organic having a polymer consisting of an acrylate compound in the main chain skeleton Polymers are particularly preferred.

  When used as a primer, the primer composition is required to have a low viscosity. More preferably, the main chain skeleton of the organic polymer (A) is made of a butyl acrylate compound to satisfy this requirement.

  It does not specifically limit as a manufacturing method of a (meth) acrylic-ester type polymer, A well-known method is mention | raise | lifted. Among these, the living radical polymerization method is preferably used because it is easy to introduce a crosslinkable functional group at the molecular chain terminal at a high ratio, and a polymer having a narrow molecular weight distribution and a low viscosity can be obtained.

  A polymer obtained by a normal free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator generally has a large molecular weight distribution value of 2 or more and tends to have a high viscosity.

  Among the methods for producing a (meth) acrylic acid ester polymer using the “living radical polymerization method”, an “atom” using an organic halide or a sulfonyl halide as an initiator and a transition metal complex as a catalyst In addition to the characteristics of “Living Radical Polymerization”, which has a narrow molecular weight distribution and a low-viscosity polymer is obtained, the “transfer radical polymerization” has a large degree of freedom in selecting initiators and catalysts, and is suitable for functional group conversion reactions. It is more preferable as a method for producing a (meth) acrylic acid ester-based polymer having a specific functional group because it has a relatively advantageous halogen at the terminal. Examples of the atom transfer radical polymerization method include Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

  The method for producing the (meth) acrylic acid ester-based polymer having a reactive silicon group is not particularly limited, and examples thereof include Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, and Japanese Patent Application Laid-Open No. Hei 6-221922. Examples thereof include a free radical polymerization method using a chain transfer agent disclosed, an atom transfer radical polymerization method disclosed in JP-A-9-272714, and the like.

  A (meth) acrylic ester copolymer comprising a plurality of the (meth) acrylic ester compounds can also be used as the main chain skeleton of the organic polymer (A).

As a specific example of the methacrylic acid ester copolymer comprising a plurality of (meth) acrylic acid ester compounds, the main chain skeleton is substantially the general formula (4):
—CH ₂ —C (R ⁵ ) (COOR ⁶ ) — (4)
(R ⁵ is a hydrogen atom or a methyl group, R ⁶ is an alkyl group having 1 to 8 carbon atoms), and a repeating unit having an alkyl group having 1 to 8 carbon atoms,
General formula (5):
—CH ₂ —C (R ⁵ ) (COOR ⁷ ) — (5)
(R ⁵ is the same as in the general formula (4). R ⁷ is an alkyl group having 9 or more carbon atoms.) A copolymer comprising a repeating unit having an alkyl group having 9 or more carbon atoms Can be given.

R ⁶ in the general formula (4) is not particularly limited as long as it is an alkyl group having 1 to 8 carbon atoms. For example, methyl group, ethyl group, propyl group, n-butyl group, t-butyl group And 2-ethylhexyl group. Among these, an alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 or 2 carbon atoms is more preferable. Note that R ⁶ contained in the copolymer is not necessarily limited to one kind of alkyl group.

R ⁷ in the general formula (5) is not particularly limited as long as it is an alkyl group having 9 or more carbon atoms, and examples thereof include lauryl group, tridecyl group, cetyl group, stearyl group, and behenyl group. Among these, an alkyl group having 10 to 30 carbon atoms is preferable, and a long-chain alkyl group having 10 to 20 carbon atoms is more preferable. Incidentally, R ⁷ contained in the copolymer is not necessarily limited to one kind of alkyl group.

  The (meth) acrylic ester copolymer is substantially composed of repeating units described in the general formula (4) and the general formula (5). Here, “substantially” means that the total proportion of the repeating units described in the general formulas (4) and (5) in the copolymer exceeds 50% by weight, and occupies the copolymer. The total proportion of the repeating units described in the general formulas (4) and (5) is preferably 70% by weight or more.

  Further, the ratio of the repeating units of the general formulas (4) and (5) present in the copolymer is preferably 95: 5 to 40:60 by weight ratio (general formula (4): general formula (5)). 90:10 to 60:40 is more preferable.

  The (meth) acrylic acid ester copolymer is a copolymer of a (meth) acrylic acid ester compound used as a repeating unit described in the general formulas (4) and (5) and a vinyl compound copolymerizable therewith. Includes coalescence.

  Examples of vinyl compounds include acrylic acid such as acrylic acid and methacrylic acid; amide groups such as acrylamide, methacrylamide, N-methylol acrylamide, and N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, diethylaminoethyl acrylate, Compounds having an amino group such as diethylaminoethyl methacrylate and aminoethyl vinyl ether; and other compounds such as acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, and ethylene.

  In the main chain skeleton of the organic polymer (A), a repeating unit other than the above, for example, having a urethane bond may be present as long as the effect of the present invention is not significantly impaired as required.

  The repeating unit having a urethane bond is not particularly limited, and examples thereof include a repeating unit having a group (hereinafter also referred to as an amide segment) generated by a reaction between an isocyanate group and an active hydrogen group.

The amide segment is general formula (6):
—NR ⁸ —C (═O) — (6)
(R ⁸ is a hydrogen atom or an organic group).

  The amide segment is not particularly limited and is, for example, a urethane group generated by a reaction between an isocyanate group and a hydroxyl group; a urea group generated by a reaction between an isocyanate group and an amino group; a group generated by a reaction between an isocyanate group and a mercapto group. And thiourethane groups.

  In the present invention, an organic group generated by a reaction of an active hydrogen in a urethane group, a urea group, and a thiourethane group with an isocyanate group is also defined as an amide segment.

A method for producing an organic polymer having a reactive silicon group having an amide segment in the main chain skeleton is not particularly limited, and examples thereof include Japanese Patent Publication No. 46-12154 (US Pat. No. 3,632,557) and Japanese Patent Publication No. 58-109529. (U.S. Pat. No. 4,374,237), JP-A-62-143030 (U.S. Pat. No. 4,645,816), JP-A-8-53528 (EP0676403), JP-A-10-204144 (EP0831108), JP-T-2003-508561 (US Pat. No. 6,1979,912) No. 6-2111879 (U.S. Pat. No. 5,364,955), JP-A No. 10-53637 (U.S. Pat. No. 5,757,751), JP-A No. 11-100197, JP-A No. 2000-169544, JP-A No. 2000-169545, JP2002-212415, Patent 331 360, U.S. Pat. No. 4,067,844, U.S. Pat. No. 3,711,445, JP-A-2001-323040, etc. are reacted with an organic polymer having an organic group having an active hydrogen at the terminal, with an excess amount of a polyisocyanate compound. Thus, after obtaining a polymer having an isocyanate group at the terminal of the polyurethane main chain, or at the same time, all or part of the isocyanate group in the polymer and the general formula (7):
_{^{W-R 9 -SiR 1 3-}} a X a (7)
(R ¹ , X, and a are the same as those in the general formula (1). R ⁹ is a divalent organic group, more preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. A method of reacting W in a silicon compound represented by a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary), which is a group having at least one active hydrogen). can give.

JP-A-11-279249 (US Pat. No. 5,990,257), JP-A 2000-119365 (US Pat. No. 6046270), JP-A 58-29818 (US Pat. No. 4345053), JP-A-3-47825 (US) Patent No. 5068304), JP-A-11-60724, JP-A-2002-155145, JP-A-2002-249538, WO03 / 018658, WO03 / 059981, and the like. Group having hydrogen and general formula (8):
O = C = N—R ⁹ —SiR ¹ _3-a X _a (8)
(R ⁹ , R ¹ , X, and a are the same as those in the general formula (1) and the general formula (7)). A method of reacting an isocyanate group of an isocyanate compound having a reactive silicon group represented by the general formula (1).

  The organic polymer having a group having an active hydrogen at the terminal is not particularly limited. For example, an oxyalkylene polymer having a hydroxyl group at the terminal (polyether polyol), a polyacryl polyol, a polyester polyol, and a saturated hydroxyl group at the terminal. A hydrocarbon polymer (polyolefin polyol), a polythiol compound, a polyamine compound and the like can be mentioned.

  Among these, polyether polyols, polyacryl polyols, and organic polymers having a polyolefin polyol component in the main chain skeleton are preferable because the glass transition temperature is relatively low and the resulting cured product is excellent in cold resistance.

  An organic polymer containing a polyether polyol component is particularly preferred because it has a low viscosity and good workability, and the resulting cured product has good deep curability and adhesiveness. In addition, a primer composition using a polyacryl polyol and an organic polymer having a saturated hydrocarbon polymer component is more preferable because the resulting cured product has good weather resistance and heat resistance.

  As the polyether polyol, those having an average of at least 0.7 hydroxyl groups per molecule are preferred.

  The production method is not particularly limited and includes known methods. For example, at least two polymerization methods using an alkali metal catalyst, at least two per molecule as an initiator in the presence of a double metal cyanide complex or cesium. Examples thereof include a polymerization method of alkylene oxide using a polyhydroxy compound having a hydroxyl group.

  Among the above polymerization methods, a polymerization method using a double metal cyanide complex has a low degree of unsaturation, a narrow molecular weight distribution (Mw / Mn), and a low-viscosity polymer can be obtained. The acid resistance and weather resistance of the resin are preferred.

  The polyacryl polyol refers to a polyol having a (meth) acrylic acid alkyl ester (co) polymer as a skeleton and having a hydroxyl group in the molecule.

  The production method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the resulting polymer has a narrow molecular weight distribution and can be reduced in viscosity. Further, a polymerization method based on a so-called SGO process in which an alkyl acrylate ester compound disclosed in JP-A-2001-207157 is continuously bulk-polymerized at high temperature and high pressure is preferable. Examples of the polyacryl polyol include Alfon UH-2000 manufactured by Toagosei Co., Ltd.

  The polyisocyanate compound is not particularly limited, and examples thereof include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. It is done.

  The silicon compound described in the general formula (7) is not particularly limited, and examples thereof include γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and γ- (N-phenyl). ) Having amino groups such as aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, etc. Silane compounds; silane compounds having a hydroxy group such as γ-hydroxypropyltrimethoxysilane; silane compounds having a mercapto group such as γ-mercaptopropyltrimethoxysilane;

  Furthermore, as the silicon compound described in the general formula (8), JP-A-6-2111879 (US Pat. No. 5,364,955), JP-A-10-53637 (US Pat. No. 5,757,751), JP-A-10-204144 (EP0831108), Michael addition reaction products of various α, β-unsaturated carbonyl compounds and silane compounds having a primary amino group disclosed in JP-A Nos. 2000-169544 and 2000-169545, or various types of (meth) Examples include a Michael addition reaction product of a silane compound having an acryloyl group and a compound having a primary amino group.

  The isocyanate compound having a reactive silicon group described in the general formula (8) is not particularly limited. For example, γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate, γ -Methyldiethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate and the like.

  Furthermore, as the isocyanate compound having a reactive silicon group described in the general formula (8), an excessive amount of the silicon compound described in the general formula (7) disclosed in JP 2000-119365 A (US Pat. No. 6,046,270) Examples include reaction products of polyisocyanate compounds.

  In order to improve the workability of the primer composition of the present invention, the viscosity of the organic polymer (A) having a reactive silicon group is preferably low. Specifically, the viscosity at 23 ° C. is preferably 30 Pa · s or less, more preferably 10 Pa · s or less, and most preferably 2 Pa · s or less. The viscosity of the organic polymer (A) can be measured using a commercially available E-type viscometer or the like.

  The primer composition of the present invention uses heavy calcium carbonate (B). Heavy calcium carbonate is obtained by mechanically crushing and processing natural chalk (chalk), limestone, marble, etc., and there are dry and wet methods. The wet pulverized product may deteriorate the storage stability of the primer composition of the present invention, and the dry pulverized product is more preferable.

  The average particle size of the heavy calcium carbonate (B) is preferably 5 μm or less, more preferably 2 μm or less, calculated from the specific surface area. There exists a tendency for the intensity | strength of hardened | cured material to increase, so that an average particle diameter is small. Moreover, there exists a tendency for the viscosity of a primer composition to become low, so that an average particle diameter is large, and it is preferable that it is 0.8 micrometer or more for this use.

  The present invention can be preferably applied when the amount of heavy calcium carbonate (B) is in the range of 30 to 200 parts by weight with respect to 100 parts by weight of the organic polymer (A). The effect of the present invention is considered to be exhibited even in the case of a blending amount exceeding 200 parts by weight, but since it is not a realistic blending, there is a possibility of lacking practicality.

  The heavy calcium carbonate (B) may be subjected to a surface treatment. Surface treatment agents used in the surface treatment of heavy calcium carbonate include organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents. It is used. Specific examples include fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, and sodium, potassium, etc. of these fatty acids. Examples thereof include salts and alkyl esters of these fatty acids. Specific examples of surfactants include polyoxyethylene alkyl ether sulfates and long-chain alcohol sulfates, sulfate anionic surfactants such as sodium salts and potassium salts thereof, alkylbenzene sulfonic acids, alkyls Examples thereof include naphthalene sulfonic acid, paraffin sulfonic acid, α-olefin sulfonic acid, alkyl sulfosuccinic acid and the like, and sulfonic acid type anionic surfactants such as sodium salt and potassium salt thereof.

  The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight, more preferably in the range of 1 to 5% by weight with respect to heavy calcium carbonate. When the treatment amount is less than 0.1% by weight, the workability and adhesion improving effect may not be sufficient, and when it exceeds 20% by weight, the storage stability of the primer composition may be lowered.

  In addition, another filler can be added to a primer composition to such an extent that the effect of invention is not impaired. These fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, Baked clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenolic resin and vinylidene chloride resin organic micro Examples thereof include fillers such as balloon, PVC powder, PMMA powder and the like; resin fillers such as asbestos, glass fibers and filaments. Among the above, surface-treated colloidal calcium carbonate is preferable. When these fillers are used, the amount used is 1 to 200 parts by weight, preferably 10 to 100 parts by weight, per 100 parts by weight of the polymer of component (A).

  As described in JP-A No. 2001-181532, the filler is uniformly mixed with a dehydrating agent such as calcium oxide, sealed in a bag made of an airtight material, and left for an appropriate time. It is also possible to dehydrate and dry in advance. By using this low water content filler, storage stability can be improved particularly when a one-component composition is used.

  When you want to obtain a hardened product with high strength by using these fillers, mainly fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment fine A filler selected from calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable, and if used in the range of 1 to 200 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive silicon group. Favorable results are obtained. In addition, when it is desired to obtain a cured product having low strength and high elongation at break, mainly calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon When a filler selected from the above is used in an amount of 5 to 200 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive silicon group, preferable results are obtained. Of course, these fillers may be used alone or in combination of two or more.

  In order to improve the workability (such as sharpness) of the composition and to make the surface of the cured product matt, it is preferable to add an organic balloon or an inorganic balloon. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5-300 μm is preferable.

  In the primer composition of the present invention, (C) an amino group-containing silane coupling agent is used. The amino group-containing silane coupling agent can greatly improve the adhesion to the base material and the adhesive component.

  Specific examples of the component (C) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldiethoxy. Silane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-amino) Ethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6-amino) Hexyl) aminopropyltrimethoxysilane, -(N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ- Aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2- Amino group-containing silanes such as aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N- (1,3-dimethylbutylidene) -3- (tri Ethoxysilyl) -1-propyl It may be mentioned ketimines type silanes such Pan'amin.

  (C) Only one type of amino group-containing silane coupling agent may be used, or a plurality of types may be used in combination. Among these, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane Is preferred.

  (C) As for the compounding quantity of an amino group containing silane coupling agent, the range of 0.1-20 weight part is preferable with respect to 100 weight part of an organic polymer (A), and is 0.5-15 weight part. It is preferably 2 to 10 parts by weight. This is because when the amount exceeds 20 parts by weight, the primer composition tends to take a long time to cure, and when it is less than 0.1 parts by weight, the effect of adhesiveness is not sufficiently exhibited.

  In the present invention, a silane coupling agent (D) having a urethane group and / or a urea group is used. The component (D) is a compound having a urethane group or urea group and a hydrolyzable silicon group in the molecule, and shows an effect of improving the adhesiveness of the cured product to various adherends when mixed, or is permeable to water vapor. This shows the effect of lowering.

Examples of the hydrolyzable silicon group present in the silane coupling agent (D) include those in which X in the general formula (1): —SiR ¹ _3-a X _a is a hydrolyzable group, Specifically, the groups already exemplified as the hydrolyzable group can be mentioned. Among these, a methoxy group, an ethoxy group, and the like are preferable because they have an appropriate hydrolysis rate. The number of hydrolyzable groups contained in one molecule of the silane coupling agent is preferably 2 or more, particularly 3 or more.

  The silane coupling agent (D) is not particularly limited. For example, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltriisopropoxysilane, γ-ureidopropylmethyldimethoxysilane, γ-ureidopropylmethyldiethoxysilane, ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, ureidomethyltriisopropoxysilane, ureidomethylmethyldimethoxysilane, ureidomethylmethyldiethoxysilane, 3-[(2-ureidoethyl) Amino] propyltrimethoxysilane, 1,3-bis [3- (trimethoxysilyl) propyl] urea, 1,3-bis [3- (triethoxysilyl) propyl] urea, 1- [3- (triethoxysilyl) ) (Lopyl) -3-phenylurea, 1,3-bis [3- (tripropylsilyl) propyl] urea, 1- [3- (triethoxysilyl) propyl] -3,3-dioctylurea, 1- [3- (Triethoxysilyl) propyl] -3,3-dihexadecylurea, 1- [3- (triethoxysilyl) propyl] -3-propylurea, 3- (3-dodecylureido) propyltriethoxysilane, N- (1 -Phenylethyl) -N '-[3- (triethoxysilyl) propyl] urea, N, N "-(methylenedi-4,1-phenylene) bis [N'-[3- (triethoxysilyl) propyl] Urea], 3,3 ′-(4,7,10-trioxatridecane-1,13-diyl) bis [1- [3- (triethoxysilyl) propyl] urea], 1- (2-anthryl) ) -3- [3- (triethoxysilyl) propyl] urea, 1- (2-anthryl) -3- [3- (triethoxysilyl) propyl] urea, 1,1 ′-[[3- (triethoxy Silyl) propylcarbamoyl] iminobisethylene] bis [3- [3- (triethoxysilyl) propyl] urea], 1,1 ′, 1 ″-[2,4,6-trioxo-1,3,5- Triazine-1,3,5-triyltris (6,1-hexanediyl)] tris [3- [3- (triethoxysilyl) propyl] urea], 1- (4-pyridinylmethyl) -3- [3- (tri Ethoxysilyl) propyl] urea, 1,10-bis [3- [3- (triethoxysilyl) propyl] ureido] decane, 1,12-bis [3- [3- (triethoxysilyl) propyl] ureido] do Decane, 1- [3- (triethoxysilyl) propyl] -3,3-bis (2-hydroxyethyl) urea, 1,3-bis [3- (methyldiethoxysilyl) propyl] urea, 1- [3 -(Triethoxysilyl) propyl] -3-allylurea, 1,1 '-(1,12-dodecandiyl) bis [3- [3- (methyldiethoxysilyl) propyl] urea], 1,1'-( 1,2-cyclohexanediyl) bis [3- [3- (triethoxysilyl) propyl] urea], N, N ″-(p-phenylenebisethylene) -N ′, N ′ ″-bis [3- (Triethoxysilyl) propyl] bisurea, 1,1 ′-(1,8-octanediyl) bis [3- [3- (triethoxysilyl) propyl] urea], 1,1 ′-(1,6- Hexanediyl) bis [3- [3 Silane coupling agents having urethane groups such as-(triethoxysilyl) propyl] urea]; methyl [3-trimethoxysilyl] propyl] carbamate, ethyl 3- (triethoxysilyl) propylcarbamate, N- [3 -(Triethoxysilyl) propyl] carbamic acid phenyl, [3- (triethoxysilyl) propyl] carbamic acid benzyl [3- (triethoxysilyl) propyl] carbamic acid 5-methyl-2- (1-methylethyl) cyclohexyl , Tris [3- (triethoxysilyl) propylcarbamic acid] 1,3,5-benzenetriyltrismethylene, 3- (triethoxysilyl) propylcarbamic acid 2- [4- (2-benzoylethenyl) phenoxy] Ethyl, [3- (triethoxysilyl) propyl] carba Octadecyl doate, tert-butyl N- [3- (triethoxysilyl) propyl] carbamate, 2- (9H-carbazol-9-yl) ethyl [3- (triethoxysilyl) propyl] carbamate, bis [[ 3- (triethoxysilyl) propyl] carbamic acid] (1,4-phenylene) bismethylene, N- [3- (triethoxysilyl) propyl] carbamic acid 2- [4- (hexyloxy) phenyl] ethenyl, bis [ Examples thereof include silane coupling agents having a urea group such as N- [3- (triethoxysilyl) propyl] carbamic acid] ethylene.

  When these silane coupling agents (D) are blended in the primer composition, only one type may be blended, or a plurality of types may be blended. Among the silane coupling agents (D), γ-ureidopropyltrimethoxysilane and γ-ureidopropyltriethoxysilane are preferable because they are easily available and have low moisture permeability.

As a compounding quantity of a silane coupling agent (D), it is preferable that it is 0.01-20 weight part with respect to 100 weight part of organic polymers (A), and it is 0.1-15 weight part. More preferred is 1 to 10 parts by weight. When the amount of the silane coupling agent (D) is less than 0.01 part by weight, the effect of improving moisture permeability and water-resistant adhesion may not be sufficiently obtained. Conversely, if the amount of the silane coupling agent (D) exceeds 20 parts by weight, practical curability may not be obtained.
(C) The total amount of the amino group-containing silane coupling agent and the silane coupling agent (D) is preferably 5 to 25 parts by weight, and particularly preferably 10 to 20 parts by weight.

  In the present invention, a silane coupling agent (E) having a long chain alkyl group having 8 or more carbon atoms is used. The component (E) is, for example, a long-chain alkyl group having a hydrolyzable silicon group bonded to one end, a long-chain alkenyl group, a cycloalkyl group or an aryl group having a long-chain alkyl group or a long-chain alkenyl group, A long-chain alkylene group having hydrolyzable silicon groups bonded to both ends, and the number of carbon atoms in the hydrocarbon portion (not including hydrocarbons forming a ring) connected on the straight chain is 8 or more, Preferably it is 8-20 hydrocarbon groups. (E) By mix | blending a component, the adhesive improvement effect with respect to various to-be-adhered bodies of hardened | cured material is shown, The effect which reduces the permeability | transmittance of water vapor | steam is shown.

  Specific examples of this long chain alkyl group include, for example, specific examples of long chain alkenyl groups such as n-octyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, cetyl group, stearyl group, and eicosyl group. As, for example, an octenyl group, nonenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, eicocenyl group, octadecadienyl group, 9,12,15-octadecatrienyl group, 9,11 , 13-octadecatrienyl group and the like.

As the hydrolyzable silicon groups present on the carbon number of 8 or more long chain alkyl groups having a silane coupling agent (E), the general formula _{^{(1): - SiR 1 3}} -a X a mentioned in Examples thereof include those in which X is a hydrolyzable group, and specific examples include the groups already exemplified as the hydrolyzable group. Among these, a methoxy group, an ethoxy group, and the like are preferable because they have an appropriate hydrolysis rate. The number of hydrolyzable groups contained in one molecule of the silane coupling agent is preferably 2 or more, particularly 3 or more.

  Specific examples of the silane coupling agent (E) having a long-chain alkyl group having 8 or more carbon atoms include, for example, n-octyltrimethoxysilane, n-decyltrimethoxysilane, n-dodecyltrimethoxysilane, n- Octadecyltrimethoxysilane, n-octyltriethoxysilane, n-dodecyltriethoxysilane, n-octadecyltriethoxysilane, n-octylmethyldimethoxysilane, n-dodecylmethyldimethoxysilane, n-octadecylmethyldimethoxysilane, n-octyl Methyldiethoxysilane, 1,8-bis (trimethoxysilyl) octane, 1,12-bis (trimethoxysilyl) dodecane, 1,8-bis (triethoxysilyl) octane, 1,12-bis (triethoxysilyl) ) Dodecane, 1,8-bis And methyl dimethoxy silyl) octane, etc., but is not limited thereto.

  When this silane coupling agent (E) having a long-chain alkyl group having 8 or more carbon atoms is blended in the primer composition, only one type may be blended or a plurality of types may be blended. Among the silane coupling agents (E), n-octyltrimethoxysilane, n-dodecyltrimethoxysilane, and n-octadecyltrimethoxysilane are preferable because they are easily available and have low moisture permeability.

As a compounding quantity of a silane coupling agent (E), it is preferable that it is 0.01-20 weight part with respect to 100 weight part of organic polymers (A), and it is 0.1-15 weight part. More preferred is 1 to 10 parts by weight. If the amount of the silane coupling agent (E) is less than 0.01 parts by weight, the effect of improving moisture permeability and water-resistant adhesion may not be sufficiently obtained. Conversely, if the amount of the silane coupling agent (E) exceeds 20 parts by weight, practical curability and adhesiveness may not be obtained.
(C) The total amount of the amino group-containing silane coupling agent and the silane coupling agent (E) is preferably 5 to 25 parts by weight, particularly preferably 10 to 20 parts by weight.

  In the primer composition of the present invention, the silane coupling agent (C) having an amino group is an essential component, the silane coupling agent (D) having a urethane group and / or a urea group, or a length having 8 or more carbon atoms. Although the silane coupling agent (E) having a chain alkyl group is used, if necessary, another silane coupling agent or a reaction product of the silane coupling agent is used as an adhesion promoter to such an extent that the effects of the present invention are not impaired. Can be added.

  The silane coupling agent and the reaction product of the silane coupling agent corresponding to the above are not particularly limited, and for example, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine Ketimine type silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanate Isocyanate silanes such as methyl) dimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylme Mercaptosilanes such as tildiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxy Epoxysilanes such as silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenyl Carboxysilanes such as bis (2-methoxyethoxy) silane and N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacrylo Vinyl-type unsaturated group-containing silanes such as luoxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxysilane, and methacryloyloxymethyltrimethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; -Isocyanurate silanes such as -trimethoxysilylpropyl) isocyanurate; Moreover, the reaction product of the said aminosilanes and epoxysilanes, the reaction product of aminosilanes and isocyanate silanes, etc. can be used. Condensates obtained by partially condensing the silanes can also be used. Furthermore, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc., which are derivatives of these, can also be used as silane coupling agents. .

  When the silane coupling agent or the reaction product of the silane coupling agent is added, the addition amount is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A). 10 to 10 parts by weight is more preferable, and 1 to 7 parts by weight is particularly preferable. If the blending amount is less than 0.01 parts by weight, the storage stability of the primer composition tends to be inferior, and the adhesiveness of the resulting cured product tends to be inferior. On the other hand, if the blending amount exceeds 20 parts by weight, there is a tendency that practical curability cannot be obtained.

  In the primer composition of the present invention, for example, an epoxy resin, a phenol resin, sulfur, an alkyl titanate, an aromatic polyisocyanate, or the like is added in order to give an adhesiveness-imparting effect. Only one kind of these may be added, or a plurality of kinds may be added in combination.

  A silicate is added to the primer composition of the present invention as necessary. The silicate acts as a crosslinking agent for the organic polymer (A), and as a result, has a function of improving the restorability, durability, and creep resistance of the resulting cured product. Further, by adding silicate, the obtained cured product is improved in adhesion and water-resistant adhesion and adhesion durability under high temperature and high humidity.

  The silicate is not particularly limited, and examples thereof include tetraalkoxysilane or a partial hydrolysis condensate thereof. More specifically, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxy Tetraalkoxysilanes (tetraalkyl silicates) such as triethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, and , And their partial hydrolysis condensates.

  When adding a silicate, as the addition amount, 0.1-20 weight part is preferable with respect to 100 weight part of organic polymers (A), 0.5-10 weight part is more preferable, 5-10 weight part Is particularly preferred.

  The partially hydrolyzed condensate of tetraalkoxysilane is not particularly limited, and examples thereof include a product obtained by adding water to tetraalkoxysilane and partially hydrolyzing and condensing it.

  It is preferable to add a partially hydrolyzed condensate of tetraalkoxysilane because the effect of improving the restoring property, durability, and creep resistance of the resulting cured product is greater than that of a primer composition to which tetraalkoxysilane is added.

  As the partially hydrolyzed condensate of tetraalkoxysilane, for example, methyl silicate 51, ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.) and the like are commercially available, and these can be used as additives.

  Further, for the purpose of preventing the surface curability of the primer composition from being changed by storage, the silicate is a reactive silicon group in which a hydrolyzable group bonded to a silicon atom is present in the organic polymer (A). It is preferable to select the same type as the hydrolyzable group. That is, when the organic polymer (A) has a methoxysilyl group, a silicate having a methoxysilyl group is selected. When the organic polymer (A) has an ethoxysilyl group, a silicate having an ethoxysilyl group is selected. Is preferred.

  In the present invention, a curing catalyst is used to obtain a primer composition. Specific examples of the curing catalyst include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate); Dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis (ethylmaleate), dibutyltin bis ( Butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (ethyl maleate), Octyltin bis (octyl maleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyltin oxide, dibutyltin bis (acetylacetonate), dioctyltin bis (acetylacetonate), dibutyltin Bis (ethyl acetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester, reaction product of dioctyltin oxide and silicate compound, dioctyltin oxide and phthalate ester Tetravalent organotin compounds such as reactants; organoaluminums such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate Compounds like; zirconium tetrakis (acetylacetonate) zirconium compounds such as and the like. Moreover, carboxylic acid and / or carboxylic acid metal salt can also be used as a curing catalyst.

  A strong base compound such as 1,8-diazabicyclo [5.4.0] undec-7-ene (abbreviated as DBU) can also be used as a curing catalyst. In particular, aryl group-containing guanidine compounds as described in WO2007 / 094276 can be suitably used because of their good adhesiveness. Examples of the aryl group-containing guanidine compound include orthotolylbiguanide and phenylguanidine, but are not limited thereto.

  As addition amount of a curing catalyst, 0.1-20 weight part is preferable with respect to 100 weight part of organic polymers (A), and 0.5-10 weight part is more preferable.

  In recent years, the toxicity of dibutyltin compounds to the human body has been pointed out. Therefore, when dibutyltin compounds are used as curing catalysts, it is preferable that the amount used is small. Specifically, the content of the dibutyltin compound contained in the primer composition is preferably 0.3% by weight or less, and more preferably 0.1% by weight or less.

  Dioctyltin compounds are less toxic than dibutyltin compounds and are preferred for use as curing catalysts. Among the dioctyltin compounds mentioned above, two of dioctyltin bis (acetylacetonate) and a reaction product of dioctyltin oxide and a silicate compound are particularly preferable. The content of the dioctyltin compound is preferably 2% by weight or less, and more preferably 1% by weight or less.

  A plasticizer can be added to the composition obtained in the present invention. By adding a plasticizer, the viscosity and slump property of the primer composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, bis (2-ethylhexyl) phthalate, butyl benzyl phthalate; non-aromatics such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate Dibasic acid esters; Aliphatic esters such as butyl oleate and methyl acetylricinolinate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Alkyldiphenyl And hydrocarbon oils such as partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

  Moreover, a polymeric plasticizer can be used. When a high-molecular plasticizer is used, the initial physical properties are maintained over a long period of time as compared with the case where a low-molecular plasticizer that is a plasticizer containing no polymer component in the molecule is used. Furthermore, the drying property (also referred to as paintability) when an alkyd paint is applied to the cured product can be improved. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester plasticizer obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; Are 1000 or more polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., or the hydroxyl groups of these polyether polyols are ester groups, ethers Polyethers such as derivatives converted into groups, etc .; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like, but are not limited thereto is not.

  Of these polymer plasticizers, those compatible with the polymer of component (A) are preferred. From this point, polyethers and vinyl polymers are preferable. Further, when polyethers are used as a plasticizer, the surface curability and deep part curability are improved, and the curing delay after storage does not occur. Polypropylene glycol is more preferred. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferred, and acrylic polymers such as polyacrylic acid alkyl esters are more preferred. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15000, more preferably 800 to 10000, still more preferably 1000 to 8000, and particularly preferably 1000 to 5000. Most preferably, it is 1000-3000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is more preferable, 1.50 or less is more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

  The number average molecular weight is measured by a terminal group analysis method in the case of a polyether polymer, and by the GPC method in the case of other polymers. Moreover, molecular weight distribution (Mw / Mn) is measured by GPC method (polystyrene conversion).

  The polymer plasticizer may not have a reactive silicon group, but may have a reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. In the case of having a reactive silicon group, the average number per molecule is preferably 1 or less, more preferably 0.8 or less. When using a plasticizer having a reactive silicon group, particularly an oxyalkylene polymer having a reactive silicon group, the number average molecular weight thereof must be lower than that of the polymer of component (A).

  A plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.

  The amount of the plasticizer used is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the polymer of component (A). If it is less than 5 parts by weight, the effect as a plasticizer is not expressed, and if it exceeds 150 parts by weight, the adhesiveness is insufficient. In order to ensure adhesiveness, the content of the plasticizer contained in the primer composition is preferably 15% by weight or less.

  A tackifier is added to the primer composition of the present invention as necessary. The tackifying resin is not particularly limited as long as it is normally used regardless of whether it is solid or liquid at room temperature. For example, a styrene block copolymer, a hydrogenated product thereof, a phenol resin, a modified phenol resin (For example, cashew oil-modified phenolic resin, tall oil-modified phenolic resin, etc.), terpene phenolic resin, xylene-phenolic resin, cyclopentadiene-phenolic resin, coumarone indene resin, rosin resin, rosin ester resin Resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.) , Hydrogenated petroleum resin, terpene resin, DCPD resin petroleum resin, etc. That. Only one kind of these may be added, or a plurality of kinds may be added in combination.

  The styrenic block copolymer and its hydrogenated product are not particularly limited. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene. Examples include butylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and styrene-isobutylene-styrene block copolymer (SIBS).

  When the tackifier is added, the addition amount is preferably 5 to 1,000 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the organic polymer (A).

  In the primer composition of this invention, a solvent or a diluent is added as needed. Solvents and diluents are not particularly limited. For example, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers Etc. Only one kind of these may be added, or a plurality of kinds may be added in combination.

  When adding a solvent or diluent, the boiling point of the solvent or diluent is preferably 150 ° C. or higher, and 200 ° C. or higher in order to prevent the volatile components from being released into the air when the primer composition is used indoors. More preferred. The amount of the solvent used is preferably as small as possible, and most preferably not used.

  A thixotropic agent (anti-sagging agent) is added to the primer composition of the present invention as necessary. The thixotropy imparting agent means one having a function of preventing the primer composition from sagging and improving workability.

  The thixotropic agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, rubber powder having a particle size of 10 to 500 μm disclosed in JP-A-11-349916 and organic fibers disclosed in JP-A-2003-155389 are exemplified. One of these thixotropic agents (anti-sagging agents) may be added, or a plurality of them may be added in combination.

  When the thixotropic agent is added, the addition amount is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A).

  In the primer composition of this invention, the compound which has an epoxy group in 1 molecule is added as needed. By adding a compound having an epoxy group, the restorability of the obtained cured product can be enhanced.

  The compound having an epoxy group is not particularly limited, and examples thereof include epoxidized unsaturated fats and oils; epoxidized unsaturated fatty acid esters; alicyclic epoxy compounds; compounds such as epichlorohydrin derivatives; and mixtures thereof. It is done. More specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate. Of these, E-PS is preferred.

  When an epoxy compound is added, the amount added is preferably 50 parts by weight or less, more preferably 5 parts by weight or less, and substantially no content with respect to 100 parts by weight of the organic polymer (A). Particularly preferred.

  An antioxidant is added to the primer composition of the present invention as necessary. By adding an antioxidant, the heat resistance of the resulting cured product can be increased.

  The antioxidant is not particularly limited, and examples thereof include hindered phenol type, monophenol type, bisphenol type, and polyphenol type antioxidants. Of these, hindered phenol antioxidants are preferred. Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by Ciba Specialty Chemicals Co., Ltd.); (All are manufactured by ADEKA Corp.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all are Sankyo Life Tech Co., Ltd.) And hindered amine light stabilizers such as Specific examples of the antioxidant are also disclosed in JP-A-4-283259 and JP-A-9-194731.

  When adding antioxidant, 0.1-10 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the addition amount, 0.2-5 weight part is more preferable.

  A light stabilizer is added to the primer composition of the present invention as necessary. Addition of the light stabilizer can prevent photooxidation deterioration of the obtained cured product.

  The light stabilizer is not particularly limited, and examples thereof include benzotriazole-based, hindered amine-based, and benzoate-based compounds. Of these, hindered amine light stabilizers are preferred.

  When adding a light stabilizer, the addition amount is preferably 0.1 to 10 parts by weight and more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the organic polymer (A). Specific examples of the light stabilizer are also disclosed in JP-A-9-194731.

  In the primer composition of this invention, the surface weather resistance of the obtained hardened | cured material improves by addition of the ultraviolet absorber with which an ultraviolet absorber is added as needed.

  The ultraviolet absorber is not particularly limited, and examples thereof include benzophenone series, benzotriazole series, salicylate series, substituted tolyl series and metal chelate series compounds. Of these, benzotriazole-based ultraviolet absorbers are preferred.

  When adding an ultraviolet absorber, 0.1-10 weight part is preferable with respect to 100 weight part of organic polymers (A), and its 0.2-5 weight part is more preferable.

  The antioxidant, light stabilizer, and ultraviolet absorber are preferably added together in the primer composition. For example, phenol-based or hindered phenol-based antioxidants, hindered amine-based light stabilizers, and benzotriazole-based ultraviolet absorbers. It is preferable to mix and add the agent.

  An epoxy resin is added to the primer composition of the present invention as necessary. Addition of an epoxy resin improves the adhesion of the resulting cured product.

  The epoxy resin is not particularly limited. For example, an epichlorohydrin-bisphenol A type epoxy resin, an epichlorohydrin-bisphenol F type epoxy resin, a flame retardant epoxy resin such as tetrabromobisphenol A glycidyl ether, a novolac type epoxy resin, or a hydrogenated bisphenol. A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various Alicyclic epoxy resin, N, N-diglycidyl aniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycerin Lumpur diglycidyl ether, glycidyl ethers of polyhydric alcohols such as glycerin, hydantoin type epoxy resins, such as epoxidized unsaturated polymer such as petroleum resins.

  Among these, those having at least two epoxy groups in one molecule are preferable because they increase the reactivity of the primer composition and the obtained cured product easily forms a three-dimensional network structure. Type epoxy resin or novolac type epoxy resin is more preferable.

  When an epoxy resin is added, the amount added depends on the intended use of the primer composition. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin, It is preferable to add 1 to 100 parts by weight of the organic polymer (A) with respect to 100 parts by weight of the resin, and it is more preferable to add 5 to 100 parts by weight. On the other hand, when improving the intensity | strength of the hardened | cured material of an organic polymer (A), it is preferable to add 1-200 weight part of epoxy resins with respect to 100 weight part of organic polymers (A), and 5-100 weight. It is more preferable to add a part.

  When an epoxy resin is added to the primer composition of the present invention, it is preferable to add a curing agent for the epoxy resin.

  The curing agent for the epoxy resin is not particularly limited as long as it is a compound capable of curing the epoxy resin. For example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylene. Primary and secondary amines such as range amine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated polyethers; 2,4,6-tris (dimethylaminomethyl) phenol, tripropylamine, etc. Tertiary amines and salts of these tertiary amines; polyamide resins; imidazoles; dicyandiamides; boron trifluoride complex compounds; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl anhydride Alcohols; 珀酸, pyromellitic anhydride, carboxylic acids such as anhydrous Kuroren acid phenol; carboxylic acids; compounds such as diketone complex compounds of aluminum or zirconium are exemplified. Only one kind of these may be added, or a plurality of kinds may be added in combination.

  The addition amount of the epoxy resin curing agent is preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Among the curing agents for epoxy resins, it is preferable to use a ketimine compound because a one-component curing composition is obtained. The ketimine compound exists stably in the absence of moisture, and is decomposed into a primary amine and a ketone by moisture, and the resulting primary amine becomes a room temperature curable curing agent for the epoxy resin. Examples of the ketimine compound include compounds obtained by a condensation reaction between an amine compound and a carbonyl compound.

  The amine compound and carbonyl compound used in the production of the ketimine compound are not particularly limited and include known compounds. Examples of the amine compound include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3- Diamines such as diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine; 1,2,3-triamino Polyamines such as propane, triaminobenzene, tris (2-aminoethyl) amine, tetrakis (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; Alkylene-based polyamines; aminosilanes such as γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; Etc.

  Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone; acetone , Aliphatic ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate , Β-dicarbonyl such as diethyl malonate, methyl ethyl malonate, dibenzoylmethane Compound; and the like.

  Ketimine compounds having an imino group include those obtained by reacting an imino group with styrene oxide; glycidyl ethers such as butyl glycidyl ether and allyl glycidyl ether; glycidyl esters and the like.

  These ketimine compounds may be added alone or in combination of two or more.

  When the ketimine compound is added, the amount added varies depending on the types of the epoxy resin and ketimine, but is usually preferably 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin.

  A flame retardant is added to the primer composition of the present invention as necessary. It does not specifically limit as a flame retardant, For example, flame retardants, such as phosphorus flame retardants, such as ammonium polyphosphate and tricresyl phosphate; Aluminum hydroxide, magnesium hydroxide, and thermally expansible graphite can be added. Only one type of flame retardant may be added, or multiple types may be added in combination.

  When adding a flame retardant, as the addition amount, 5-200 weight part is preferable with respect to 100 weight part of organic polymers (A), and 10-100 weight part is more preferable.

  In the primer composition of the present invention, various additives other than those described above are added as necessary for the purpose of adjusting various physical properties of the primer composition or the cured product obtained. Such additives include, for example, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, anti-anticides, Examples include fungicides. Specific examples thereof are disclosed in JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, JP-A-2001-72854, and the like. ing. Moreover, these additives may add only 1 type and may add it in combination of multiple types.

  When the primer composition is a one-component type, since all the compounding components are preliminarily blended, curing may proceed during storage if moisture exists in the blend. Therefore, it is preferable to add the moisture-containing blending component after dehydrating and drying in advance, or dehydrating it during decompression or the like during blending and kneading.

  When the primer composition is of a two-component type, it is not necessary to add a curing catalyst to the main agent containing an organic polymer having a reactive silicon group, so that the curing proceeds even if the composition contains some moisture ( There is little concern about gelation, but when long-term storage stability is required, dehydration and drying are preferred.

  As the dehydration and drying method, use heat drying method or vacuum dehydration method when the compound is a solid such as powder, and use vacuum zeolite dehydration method or synthetic zeolite, activated alumina, silica gel, quick lime, magnesium oxide, etc. The dehydration method is preferred. Further, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxy An alkoxysilane compound such as silane; an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine; or an isocyanate compound added to the primer composition, Also preferred is a dehydration method carried out by reacting with water contained in the water. Thus, the storage stability of the primer composition is improved by adding an alkoxysilane compound, an oxazolidine compound, and an isocyanate compound.

  As an addition amount when using an alkoxysilane compound that can react with water such as vinyltrimethoxysilane for the purpose of drying, 0.1 to 20 parts by weight is preferable with respect to 100 parts by weight of the organic polymer (A). 0.5-10 weight part is more preferable.

  The method for preparing the primer composition of the present invention is not particularly limited. For example, the above-described compounding ingredients are prepared and kneaded using a mixer, roll, kneader, etc. at room temperature or under heating, and a small amount of a suitable solvent. A known method such as a method of dissolving the compounding components after use and mixing them may be employed.

When exposed to the atmosphere, the primer composition of the present invention forms a three-dimensional network structure by the action of moisture, and cures to a solid having rubbery elasticity.
The primer composition of the present invention can be suitably used as a coating material or primer because it has low viscosity, no solvent, and good adhesion. In particular, it is useful as a primer for improving the adhesion between a concrete substrate and a floor adhesive for interior use.

  The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

(Synthesis Example 1)
Add 1.2 times equivalent of NaOMe methanol solution to the hydroxyl group of polyoxypropylene diol with molecular weight of about 3,000 to distill off methanol, and then add allyl chloride to convert the terminal hydroxyl group to an allyl group. did. Unreacted allyl chloride was removed by devolatilization under reduced pressure. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl-terminated polypropylene oxide, water was removed by centrifugation, and water was further added to the resulting hexane solution. After 300 parts by weight of the mixture were mixed and stirred, water was removed again by centrifugation, and then hexane was removed by devolatilization under reduced pressure.

100 parts by weight of the allyl group-terminated polypropylene oxide was reacted with 6.0 parts by weight of methyldimethoxysilane at 90 ° C. for 2 hours using 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst. Silyl group-terminated polypropylene oxide (A-1) was obtained. ^{When 1} H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL Ltd.) was measured, the average number of terminal methyldoxysilyl groups was 1.6 per molecule. When the viscosity at 23 ° C. of the organic polymer (A-1) having a molecular weight of 3,000 and having a methyldimethoxysilyl group at the terminal was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd .; Model RE80). 0.64 Pa · s.

(Synthesis Example 2)
Polyoxypropylene triol having a molecular weight of about 3,000 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of 16,400 (using a Tosoh HLC-8120GPC as a liquid feeding system, The column used TSK-GEL H type manufactured by Tosoh, and the solvent obtained was a polystyrene oxide (polystyrene equivalent molecular weight measured using THF). Subsequently, a methanol solution of 1.2 times equivalent NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by devolatilization under reduced pressure. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl-terminated polypropylene oxide, water was removed by centrifugation, and water was further added to the resulting hexane solution. After 300 parts by weight of the mixture were mixed and stirred, water was removed again by centrifugation, and then hexane was removed by devolatilization under reduced pressure.

100 parts by weight of the obtained allyl group-terminated polypropylene oxide was reacted with 1.8 parts by weight of methyldimethoxysilane at 90 ° C. for 2 hours using 150 ppm of an isopropanol solution containing 3 wt% platinum as a platinum vinylsiloxane complex as a catalyst. Silyl group-terminated polypropylene oxide (A-2) was obtained. When ¹ H-NMR was measured by the same method as in Synthesis Example 1, the number of terminal methyldoxysilyl groups averaged 2.1 per molecule. The viscosity at 23 ° C. of the organic polymer (A-2) having a molecular weight of 16,400 and having a methyldimethoxysilyl group at the end was measured to be 8.5 Pa · s.

(Examples 1-2, Comparative Examples 1-2)
With respect to 100 parts by weight of the organic polymer (A-1) having a reactive silicon group obtained in Synthesis Example 1, 135 parts by weight of heavy calcium carbonate (made by Imerys, trade name: Carbital 110) was weighed. Well dispersed and mixed. To this, tetraethyl silicate (manufactured by Evonik, trade name: Dynasylan A) 7 parts by weight, aminopropyltrimethoxysilane (manufactured by Evonik, trade name: Dynasylan AMMO) 7 parts by weight, ureidopropyltrimethoxysilane (manufactured by Momentive), Product name: SILQUEST A-1524 Silane), vinyltrimethoxysilane (Evonik, product name: Dynasylan VTMO) 2 parts by weight, a mixture of dioctyltin oxide and ethyl silicate as a curing catalyst (product name, manufactured by Nitto Kasei Co., Ltd.) : Neostan S-1) 1 part by weight was weighed and mixed using a rotation / revolution mixer (manufactured by Shinky Co., Ltd., trade name: Nertaro Awatori) to obtain a primer composition.

(Example 2)
A primer composition in the same manner as in Example 1 except that 7 parts by weight of n-octyltrimethoxysilane (manufactured by Evonik, trade name: Dynasylan OCTMO) was used instead of ureidopropyltrimethoxysilane in Example 1. Got.

(Comparative Example 1)
A primer composition was obtained in the same manner as in Example 1 except that ureidopropyltrimethoxysilane in Example 1 was not used.

(Comparative Example 2)
Implementation was performed except that the amount of tetraethyl silicate used in Example 1 was changed to 12.5 parts by weight, the amount of aminopropyltrimethoxysilane was changed to 12.5 parts by weight, and ureidopropyltrimethoxysilane was not used. A primer composition was obtained in the same manner as in Example 1.

  The surface of the primer composition obtained above was evaluated for curing time, moisture permeability, and adhesion to concrete under constant temperature and humidity conditions of 23 ° C. and 50%. The primer composition was molded into a sheet of about 2 mm thickness and cured and cured for 7 days, and the moisture permeability was measured. The obtained results are shown in Table 1.

(Surface curing time)
The primer composition is stretched to a thickness of about 3 mm under conditions of 23 ° C. and 50% RH, and the surface of the primer composition is lightly touched over time using a microspatula, so that the composition does not adhere to the microspatula. The time until was measured.

(Amount of water vapor that has passed through the cured product in a thin layer)
The primer composition was molded into a thin sheet having a thickness of about 2 mm under conditions of 23 ° C. and 50% RH, and cured for 7 days. This thin sheet was brought into close contact with the upper part of a glass container in which water was put, and was placed in a desiccator under 23 ° C. conditions. A sufficient amount of dried silica gel was placed at the bottom of the desiccator. An outline of the evaluation method is shown in FIG. The weight of the whole cup was measured after the initial, 1 week, 4 weeks, and 12 weeks, and the reduced values are shown in Table 1. The reduced value was taken as the amount of water vapor permeating through the cured film.

(Adhesion to concrete)
The primer composition was applied on a concrete substrate with a thickness of about 2 mm, and cured and cured under conditions of 23 ° C. and 50% RH for 24 hours. Thereafter, the following floor adhesive was applied in a bead shape, and curing curing was performed for 7 days under the same conditions. The bead-like cured product was cut and pulled to evaluate adhesion. Further, another bead-like cured product was immersed in water and soaked for 7 days, and then the cured product was similarly cut and pulled to evaluate adhesion. The adhesion state is indicated by C when the adhesive layer is cohesive failure, and A when the adhesive layer is interfacial failure, and indicates that the cohesive failure is better. When cohesive failure and interfacial failure were mixed, the respective ratios were indicated by numerical values so that the total was 100. That is, C50A50 represents a state where the cohesive failure is 50% and the interface failure is 50%.

  The floor adhesive used for the above adhesive evaluation was prepared based on the following formulation.

  100 parts by weight of the organic polymer (A-2) having a reactive silicon group obtained in Synthesis Example 2, 250 parts by weight of surface-treated heavy calcium carbonate (made by Omya, trade name: Hydrocarb 95T), polypropylene having a molecular weight of 2000 Three paint rolls were prepared by mixing 50 parts by weight of glycol (manufactured by Bayer, trade name: ACCLAIM2200) and 2 parts by weight of an amide wax-based sagging inhibitor (manufactured by Cray Valley, trade name: Crayvallc SLX). And dispersed three times. Thereafter, dehydration under reduced pressure at 120 ° C. for 2 hours, cooling to 50 ° C. or lower, and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane (manufactured by Evonik, trade name: Dynasylan DAMO) as an adhesion-imparting agent 1.5 parts by weight, 1.5 parts by weight of aminopropyltrimethoxysilane (manufactured by Evonik, trade name: Dynasylan AMMO), 2 parts by weight of vinyltrimethoxysilane (manufactured by Evonik, trade name: Dynasylan VTMO), curing catalyst After adding 1 part by weight of a mixture of dioctyltin oxide and ethyl silicate (trade name: Neostan S-1 manufactured by Nitto Kasei Co., Ltd.), kneading in a substantially moisture-free state, The container, which is a container, was sealed and a one-component floor adhesive was obtained.

  As is apparent from Table 1, an organic polymer (A) having a reactive silicon group, heavy calcium carbonate (B), a silane coupling agent (C) having an amino group, a silane cup having a urethane group or a urea group When the ring agent (D) and / or the silane coupling agent (E) having a long-chain alkyl group having 8 or more carbon atoms is used, the water vapor permeability is low when it is made into a thin layer. Adhesion was improved.

Claims (7)

(A) an organic polymer having a silicon group that can be crosslinked by forming a siloxane bond, (B) heavy calcium carbonate, (C) a silane coupling agent having an amino group, (E) having 8 or more carbon atoms a silane coupling agent having a long chain alkyl group, only containing primer compositions construction concrete foundation. The primer composition according to claim 1, wherein the main chain skeleton of the organic polymer (A) is a polyoxyalkylene polymer and / or a (meth) acrylic acid ester polymer. The primer composition of Claim 1 or Claim 2 whose content rate of the dibutyltin compound contained in a primer composition is 0.3 weight% or less. The primer composition according to any one of claims 1 to 3 , wherein the curing catalyst contained in the primer composition is a dioctyltin compound. The primer composition in any one of Claims 1-4 whose content rate of the plasticizer contained in a primer composition is 15 weight% or less. The primer composition according to any one of claims 1 to 5, wherein the primer composition is used between a concrete base and an adhesive for flooring. The primer composition according to any one of claims 1 to 6, further comprising (D) a silane coupling agent having a urethane group and / or a urea group.