JP2014105267A - Primer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer composition that suppresses curing delay on an adhesive interface and accelerates to develop adhesion and has excellent adhesiveness.SOLUTION: A composition of the invention comprises: a chlorinated polymer (B); a diisocyanate compound (C); a polyisocyanate compound (D); a silane coupling agent having mercapto group (E); and a catalyst (F). The solvent (A), the chlorinated polymer (B), the diisocyanate compound (C), the silane coupling agent having mercapto group (E), and the catalyst (F) are mixed and then the polyisocyanate compound (D) is mixed into the resultant mixture to obtain a primer composition. The composition of the invention suppresses curing delay on an adhesive interface between the primer and a novel sealing material, and accelerates to develop adhesion to improve adhesiveness.

Description

  The present invention relates to a primer composition.

  Sealing materials are widely used in buildings and the like for filling joints and gaps between various members and ensuring watertightness and airtightness. Typical building sealants include one-pack or two-pack sealants such as silicone sealants, modified silicone sealants, polyurethane sealants, polysulfide sealants, and the like.

  Architectural sealing materials are required to exhibit adhesion to difficult-to-adhere coating surfaces such as acrylic electrodeposition coating surfaces and fluorine coating surfaces. In addition, a primer composition is used to improve the adhesion between the adherend and the sealing material (see, for example, Patent Document 1).

  Patent Document 1 describes a primer composition that can follow even a thin adherend and has excellent adhesion to the adherend. In the primer composition described in Patent Document 1, a predetermined amount of a synthetic product (A) obtained by reacting mercaptosilane with a thiourethane reaction with an adduct obtained by adding diisocyanate to a trimethylolpropane (TMP) end, and a chlorinated polymer ( B), a diisocyanate compound (C), a curing catalyst (D), and a solvent (E) are contained.

  In addition, after applying the sealing material, it may be necessary to repair the construction portion due to deterioration of the sealing material or the like. At this time, after removing the existing sealing material (advanced sealing material) from the joints, the primer is applied and a new sealing material (advanced sealing material) is applied. It may not be possible to remove, and it may be necessary to splice the post-sealing sealant to the pre-sealant.

JP 2011-201994 A

  However, when a new sealant (post-sealing sealant) is used for installation, if the pre-sealant remains, curing delays at the interface between the primer and the new sealant, resulting in joint movement. A new sealing material sometimes peeled off.

  Therefore, a primer composition that has a rapid adhesion development without causing a delay in curing at the adhesion interface between the primer and the new sealing material is desired.

  An object of this invention is to provide the primer composition which suppresses the cure delay in an adhesion interface, accelerates | stimulates adhesion development, and is excellent in adhesiveness in view of the said problem.

The present invention includes the following (1) to (6).
(1) solvent (A),
A chlorinated polymer (B);
A diisocyanate compound (C);
A polyisocyanate compound (D);
A silane coupling agent (E) having a mercapto group;
A catalyst (F),
Including
After mixing the solvent (A), the chlorinated polymer (B), the diisocyanate compound (C), the silane coupling agent (E) having the mercapto group, and the catalyst (F), the polyisocyanate compound. A primer composition obtained by mixing (D).
(2) solvent (A),
A chlorinated polymer (B);
A diisocyanate compound (C);
A polyisocyanate compound (D);
A silane coupling agent (E) having a mercapto group;
A catalyst (F),
Including
The primer composition, wherein the diisocyanate compound (C) is an aromatic diisocyanate compound.
(3) The primer composition according to (1) or (2), wherein the catalyst (F) is a tin-based catalyst.
(4) The primer composition according to any one of (1) to (3), which is used for a two-component modified silicone sealant.
(5) The primer composition according to any one of (1) to (4), which is used for joining a sealing material and a sealing material.
(6) The primer composition according to (4) or (5) above, wherein the sealing material contains an organic polymer having a hydrolyzable silicon-containing group.

  According to the present invention, it is possible to suppress curing delay at the adhesion interface and promote adhesion development.

FIG. 1 is a perspective view showing a state of a peel test (peel test).

  The present invention will be described in detail below. The present invention is not limited by the following modes for carrying out the invention (hereinafter referred to as embodiments). In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range. Furthermore, the constituent elements disclosed in the following embodiments can be appropriately combined.

  The primer composition according to the present embodiment (hereinafter referred to as “the composition of the present embodiment”) includes a solvent (A), a chlorinated polymer (B), a diisocyanate compound (C), a polyisocyanate compound ( D), a silane coupling agent (E) having a mercapto group, and a catalyst (F), a solvent (A), a chlorinated polymer (B), a diisocyanate compound (C), and a silane cup having a mercapto group A primer composition obtained by mixing a ring agent (E) and a catalyst (F) and then mixing a polyisocyanate compound (D).

<Solvent (A)>
The solvent (A) contained in the composition of the present embodiment includes a chlorinated polymer (B), a diisocyanate compound (C), a polyisocyanate compound (D), and a silane coupling agent (E) having a mercapto group. In addition, conventionally known various solvents can be used as long as they are inert to the catalyst (F). There is no restriction | limiting in particular as a solvent (A), A well-known thing, such as an organic solvent and a water-soluble solvent, can be used. Specific examples of the solvent (A) include hydrocarbons such as benzene, toluene, xylene, hexane, heptane, octane and cyclohexane; halogenated hydrocarbons such as tetrachloromethane and methylene chloride; acetone and methyl ethyl ketone. , Ketone systems such as methyl isobutyl ketone and cyclohexanone; ether systems such as diethyl ether, tetrahydrofuran and dioxane; ester systems such as methyl acetate, ethyl acetate and butyl acetate; ether ester systems such as cellosolve acetate and butylcellosolve acetate; methanol, ethanol, Alcohols such as propanol, i-propanol and n-butanol; petroleums ranging from gasoline such as mineral spirits to kerosene fractions; in addition, N-methyl-2-pyrrolidone, N, N-dimethylform Bromide, dimethyl acetamide, and the like. These solvents may be used alone or in combination of two or more.

  Among these, methyl ethyl ketone and ethyl acetate are preferable because the bonding speed and workability are improved. The solvent is preferably used after sufficiently dried or dehydrated.

  It is preferable that content of the said solvent (A) is 60 to 95 mass% with respect to the total mass (total mass) of the composition of this embodiment. If content of a solvent (A) is this range, favorable applicability | paintability can be obtained.

  The content of the solvent (A) in the composition of the present embodiment can be appropriately changed according to the use, purpose, etc. of the composition.

<Chlorinated polymer (B)>
The chlorinated polymer (B) contained in the composition of the present embodiment is not particularly limited as long as it is a chlorinated polymer. Preferably, for example, a chlorinated product of isoprene-based synthetic rubber, chlorinated polyethylene, chlorine Chlorinated polypropylene, chlorinated polyethylene / propylene copolymer, chlorinated polybutadiene, chlorinated polystyrene, chlorinated polybutadiene / styrene copolymer, chlorosulfonated polyethylene, chlorosulfonated polyethylene / vinyl acetate copolymer, etc. The The chlorinated polymer (B) may be used in combination of two or more chlorinated polymers exemplified above.

  The chlorination rate of the chlorinated polymer (B) is preferably from 5% to 70%, more preferably from 10% to 70%, particularly preferably from 40% to 70%. When the chlorination rate is 40% or more and 70% or less, excellent properties are exhibited in both adhesiveness and workability. The chlorination rate is a value measured by fluorescent X-ray analysis.

  The number average molecular weight (Mn) of the chlorinated polymer (B) is not particularly limited, but is preferably about 10,000 to 1,000,000. Particularly, if it is about 20,000 to 500,000, it has moderate strength and stability. From the viewpoint of adhesion stability. Furthermore, the molecular weight distribution (mass average molecular weight Mw / number average molecular weight Mn) is preferably as narrow as possible because the viscosity at the same molecular weight is low.

  Content of a chlorinated polymer (B) is 1 to 50 mass% with respect to the total mass (total mass) of a composition, Preferably it is 3 to 40 mass%.

  When content of a chlorinated polymer (B) is in the said range, adhesiveness will improve and the adhesive stability of the composition of this embodiment will improve. Adhesive stability falls that content of a chlorinated polymer (B) is less than 1 mass%. On the other hand, even if the content of the chlorinated polymer (B) is more than 50% by mass, the adhesiveness is lowered, which is not preferable.

<Diisocyanate compound (C)>
The diisocyanate compound (C) contained in the composition of the present embodiment is not particularly limited as long as it has two isocyanate groups (NCO groups) in the molecule. Specific examples of the diisocyanate compound (C) include paraphenylene diisocyanate, tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2, Aromatic isocyanates such as 4′-diphenylmethane diisocyanate (2,4′-MDI) and tolidine diisocyanate (TODI); tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate ( NBDI), aliphatic isocyanates such as octadecyl diisocyanate; transcyclohexane-1,4-diisocyanate, isophorone diisocyanate Examples include cycloaliphatic isocyanates such as anate (IPDI) and dicyclohexylmethane diisocyanate (H ₁₂ MDI); aryl aliphatic isocyanates such as xylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI); It is done. These can be used individually by 1 type or in combination of 2 or more types, respectively.

  Among these, preferably aromatic isocyanates and aliphatic isocyanates can be used, and more preferably aromatic isocyanates can be suitably used. As the aromatic isocyanate, diphenylmethane diisocyanate (MDI) or tolylene diisocyanate (TDI) is preferably used. As the aliphatic isocyanate, xylene diisocyanate (XDI) or hexamethylene diisocyanate (HDI) is preferably used. These can be used individually by 1 type or in combination of 2 or more types, respectively.

  Conventionally, when the diisocyanate compound (C) is an aliphatic isocyanate, the diisocyanate compound (C), a silane coupling agent (E) having a mercapto group described later, and a polyisocyanate compound (D) described later When they were mixed at the same time, a curing delay occurred at the adhesion interface between the primer composition and the new sealing material, and the adhesion was delayed and the sealing material did not cure. On the other hand, the composition of this embodiment mixes the diisocyanate compound (C) and the silane coupling agent (E) which has a mercapto group mentioned later first, from the polyisocyanate compound (D) mentioned later. Since the unreacted isocyanate group in the diisocyanate compound (C) can be reduced by reacting first, the curing delay at the adhesion interface between the primer composition and the sealing material is suppressed, and the development of adhesion is promoted. can do.

  Further, when the diisocyanate compound (C) contains an aromatic diisocyanate or is an aromatic diisocyanate, the diisocyanate compound (C) and the polyisocyanate are more reactive than the polyisocyanate compound (D) described later. Even if the compound (D) and the silane coupling agent (E) having a mercapto group are mixed at the same time, the diisocyanate compound (C) and the silane coupling agent (E) having a mercapto group described below are preferentially reacted. be able to. Therefore, since the unreacted isocyanate group in the diisocyanate compound (C) can be reduced, the curing delay at the adhesion interface between the primer composition and the sealing material can be suppressed, and adhesion development can be promoted.

  The content of the diisocyanate compound (C) is preferably 0.5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the solvent (A).

  When the content of the diisocyanate compound (C) is within the above range, the composition of the present embodiment can suppress curing delay at the adhesion interface and is excellent in curability.

  When the diisocyanate compound (C) contains two or more diisocyanate compounds, the content of the aromatic diisocyanate compound in the diisocyanate compound (C) is 1% by mass or more and 100% by mass or less in the total amount of the diisocyanate compound (C). preferable. When the content of the aromatic diisocyanate compound is within the above range, the composition of the present embodiment can suppress curing delay at the adhesion interface and is excellent in curability.

<Polyisocyanate compound (D)>
The polyisocyanate compound (D) contained in the composition of the present embodiment is not particularly limited as long as it has two or more isocyanate groups in the molecule. As the polyisocyanate compound (D) having two isocyanate groups in the molecule, the same as the diisocyanate compound (C) can be used. Examples of the polyisocyanate compound (D) other than the diisocyanate compound (C) include aromatic polyisocyanates such as polymethylene polyphenylene polyisocyanate and triphenylmethane triisocyanate; hexamethylene diisocyanate (HDI), trimethylhexamethylene. Aliphatic polyisocyanates such as diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); alicyclic polyisocyanates such as bis (isocyanatomethyl) cyclohexane (H ₆ XDI); the above diisocyanate compound (C) And a carbodiimide-modified polyisocyanate of the polyisocyanate compound (D); the diisocyanate compound (C) and the polyisocyanate Isocyanurate modified polyisocyanate of sulfonate compound (D) can be mentioned. Such polyisocyanate compounds can be used singly or in combination of two or more.

  Specific examples of the polyisocyanate compound (D) having three or more isocyanate groups include tris (phenyl isocyanate) thiophosphate, polymethylene polyphenyl isocyanate, and a polyisocyanate compound having an isocyanurate ring. It is done. These can be used individually by 1 type or in combination of 2 or more types, respectively.

  Other polyisocyanate compounds (D) include polyisocyanate adducts obtained by reacting the above polyisocyanate compounds with compounds such as trimethylolpropane (TMP), adducts of polyisocyanate compounds, biuret bodies, isocyanates. A nurate body etc. are also mentioned. Hereinafter, such a polyisocyanate compound (D) is referred to as an “isocyanate adduct”.

  As such an isocyanate adduct, specifically, for example, an HDI-TMP adduct obtained by reacting HDI with TMP, an XDI-TMP adduct obtained by reacting XDI with TMP, and TDI with TMP. TDI-TMP adduct obtained by reaction, TMXDI-TMP adduct obtained by reacting TMXDI with TMP, HXDI-TMP adduct obtained by reacting HXDI with TMP, obtained by reacting IPDI with TMP Examples include IPDI-TMP adduct, HDI biuret, HDI isocyanurate, IPDI isocyanurate, TDI isocyanurate, and the like. Among these, a TDI-TMP adduct obtained by reacting TDI with TMP can be preferably exemplified.

  The polyisocyanate compound (D) contained in the composition of this embodiment is preferably the above-mentioned isocyanate adduct. When the polyisocyanate compound (D) is a polyisocyanate adduct, the reactivity is lower than that of the diisocyanate compound (C) described above, and therefore the diisocyanate compound (C) and a silane coupling agent (E) having a mercapto group described later. Can be made to react prior to the reaction with the polyisocyanate compound (D). Thereby, since the unreacted isocyanate group in a diisocyanate compound (C) can be reduced, the cure delay in the adhesion interface of a primer composition and a sealing material can be suppressed, and adhesion expression can be promoted.

  As a commercial item of the above-mentioned isocyanate adduct, for example, TDI-TMP adduct which is an aromatic polyisocyanate (Sumidur L-75, NCO group content 13.0% by mass, manufactured by Sumika Bayer Urethane Co., Ltd.), etc. Can be suitably used.

  Content of a polyisocyanate compound (D) is 100 to 1000 mass parts with respect to 100 mass parts of diisocyanate compound (C), Preferably it is 300 to 700 mass parts.

  When the content of the polyisocyanate compound (D) is within this range, adhesion is fast and sufficient adhesion is obtained.

<Silane coupling agent (E) having a mercapto group>
The silane coupling agent (E) contained in the composition of this embodiment will not be specifically limited if it is a silane coupling agent which has a mercapto group in a molecule | numerator. As a silane coupling agent (E), what has a mercapto group in a molecule | numerator from a viewpoint of promoting adhesion | attachment expression is preferable.

  Specific examples of the silane coupling agent (E) having a mercapto group include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropylmethyl. Examples include mercapto group-containing silane compounds such as diethoxysilane. Among these, γ-mercaptopropyltrimethoxysilane is preferably used. These silane coupling agents may be used singly or in combination of two or more.

  The composition of this embodiment can contain other silane coupling agents other than the silane coupling agent (E) which has a mercapto group. Specific examples of other silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and other epoxy group-containing silane compounds;

  γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N- amino group-containing silane compounds such as β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; γ-ureido Ureido group-containing silane compounds such as propyltrimethoxysilane and 3-ureidopropyltriethoxysilane;

  (Poly) sulfide group-containing silane compounds such as bis (triethoxysilylpropyl) tetrasulfide and bis (triethoxysilylpropyl) disulfide; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) Silane-containing vinyl group-containing silane compounds; γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, etc. Silane compounds;

  Carboxysilane compounds such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; Trimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatoethyltrimethoxysilane, γ-isocyanatoethyltriethoxysilane, γ-isocyanateethylmethyl Isocyanate group-containing silane compounds such as diethoxysilane and γ-isocyanatoethylmethyldimethoxysilane; N- (1,3-dimethylbutylidene) -3- (trimethoxy) Silyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (methyldimethoxy) Silyl) -1-propanamine, ketimine group-containing silane compounds such as N- (1,3-dimethylbutylidene) -3- (methyldiethoxysilyl) -1-propanamine; γ-chloropropyltrimethoxysilane and the like; Halogen-containing silane compounds; silyl esters such as methyl silyl esters; silane compounds such as orthosilicate esters and the like. These silane coupling agents may be used singly or in combination of two or more.

  Among the above silane coupling agents, mercapto group-containing silane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropylmethyldiethoxysilane are particularly preferred. It is preferably mentioned because it exhibits fast adhesion and is excellent in the effect of improving the adhesion at the joint surface.

  As the silane coupling agent (E) contained in the composition of the present embodiment, a mercapto group-containing silane compound is preferably used in terms of rapid adhesion development and excellent adhesion.

  Further, when the functional group bonded to silicon of the silane coupling agent is a methoxy group, the reactivity is faster than that of the ethoxy group. Therefore, the functional group bonded to silicon of the silane coupling agent is an ethoxy group. More preferred is a methoxy group.

  The functional group bonded to silicon in the silane coupling agent is more preferably a dimethoxy group or a trimethoxy group. When the functional group is a methoxy group, the adhesion with the modified silicone sealant can be improved.

  A commercial item may be used for said silane coupling agent, and you may manufacture it. Manufacturing conditions are not particularly limited, and can be performed by known methods and conditions.

  The amount of the diisocyanate compound (C) and the silane coupling agent (E) having a mercapto group is such that the equivalent ratio of the isocyanate group to the thiol group (SH group) (NCO group / SH group) is 0.5 or more and 2.5. The following is preferable, and 0.5 or more and 2.0 or less are more preferable.

  If the content of the silane coupling agent (E) having a mercapto group is within the above range, the adhesion to the adhesive interface between the primer composition and the new sealing material is improved without adversely affecting the physical properties of the cured product. Can be made.

<Catalyst (F)>
The composition of the present embodiment contains the catalyst (F), so that the adhesion development is accelerated and sufficient adhesiveness is obtained even for the joining surface of the sealing material. In the composition of the present embodiment, the catalyst (F) can be used as a curing agent for the chlorinated polymer (B). The catalyst (F) contained in the composition of the present embodiment is not particularly limited as long as it can react with the curable resin.

  As the catalyst (F) contained in the composition of the present embodiment, a metal catalyst, a tin catalyst, an amine catalyst, and the like can be given in that the adhesion promoting effect is excellent.

  Examples of the metal catalyst, tin catalyst, and amine catalyst include organometallic compounds, tertiary amines, salts of tertiary amines and carboxylic acids, and the like. Specifically, examples of the organometallic compound include divalent tin compounds such as tin octoate, tin octylate, tin butanoate, tin naphthenate, tin caprylate and tin oleate; dibutyltin dioctoate, dibutyl Tin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dibutyltin dioleate, dioctyltin dilaurate, dioctyltin diversate, diphenyltin diacetate, dibutyltin dimethoxide, dibutyltin oxide, dibutyltin bis (triethoxysilicate), Tetravalent organotin compounds such as reaction products of dibutyltin oxide and phthalates; dibutyltin bis (acetylacetonate), tin-based chelate compounds, zirconium tetrakis (acetylacetonate), titanium tetrakis (acetate) Ruacetonate), aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetone nickel, acetylacetone zinc, acetylacetone manganese, and the like; Titanates such as tetra-n-butyl titanate and tetrapropyl titanate; and other metals other than tin such as manganese, iron, cobalt, copper, zinc, zirconium, lead, bismuth, such as lead octylate and zirconium octylate And metal organic acid salts with various organic acids such as octylic acid, stearic acid, and naphthenic acid. Examples of amines include primary amines such as butylamine, hexylamine, octylamine, dodecylamine, oleylamine, cyclohexylamine and benzylamine; secondary amines such as dibutylamine; diethylenetriamine, triethylenetetramine and guanidine. , Polyphenyls such as diphenylguanidine, xylylenediamine; triethylenediamine, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo [5,4,0] -7-undecene Cyclic amines; amino alcohol compounds such as monoethanolamine, diethanolamine and triethanolamine; amines such as aminophenol compounds such as 2,4,6-tris (dimethylaminomethyl) phenol Quaternary ammonium salts such as benzyltriethylammonium acetate; low molecular weight amide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound, etc. Is mentioned. In addition, triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,4-diazabicyclo [2,2,2] octane (DABCO), Tertiary amines such as N-methylmorpholine and N-ethylmorpholine, or salts of these amines with carboxylic acid and the like. These catalysts can be used singly or in combination of two or more.

  Among these, a tin-based catalyst and an amine-based catalyst are preferable, and a tin-based catalyst is particularly preferable from the viewpoint of having a large amount of catalytic ability. Either or both of a tin-based catalyst and an amine-based catalyst may be used. As the tin-based catalyst, either divalent or tetravalent may be used, or both may be used in combination. As the amine catalyst, tertiary amines are preferably used.

  As a tin-based catalyst contained in the composition of the present embodiment, from the viewpoint that adhesion development can be promoted, dialkyltin oxide such as dibutyltin oxide and dioctyltin oxide, and ester compounds such as dioctylphthalate, diisodecylphthalate, and methyl maleate (For example, trade names “MSCAT-01” and “MSCAT-02”, which are DINP-modified tin catalysts, manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name “No. 918”: Sansha Co., Ltd.) Product).

  Content of the said catalyst (F) is 1.0-5.0 mass parts with respect to 100 mass parts of diisocyanate compounds (C), Preferably it is 1.5-3.0 mass parts. .

  When the content of the catalyst (F) is within the above range, the composition of the present embodiment exhibits rapid adhesion, and sufficient adhesiveness is obtained for the joining surface of the sealing material.

  In the present embodiment, by using the catalyst (F), the adhesion reaction speed with the sealing material can be increased, and the progress of the adhesion reaction can be promoted to shorten the working time for adhesion. Moreover, by using a tin-based catalyst as the catalyst (F), adhesion development can be promoted, and initial adhesiveness to the joining surface of the sealing material can be improved.

  The composition which concerns on this embodiment can contain various additives other than each component mentioned above as needed in the range which does not impair the objective of this invention. Examples of additives include fillers, plasticizers, pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion promoters, stabilizers, and dispersants. Two or more of these may be contained. The additives and the like can be kneaded by a general method to obtain a composition, which can be used for vulcanization or crosslinking. The blending amounts of these additives can be conventional conventional blending amounts as long as the object of the present embodiment is not violated.

  Examples of the filler include organic or inorganic fillers having various shapes. Specifically, for example, wax stone clay, kaolin clay, calcined clay; silica sand, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; calcium carbonate, heavy calcium carbonate, precipitated calcium carbonate (Light calcium carbonate), colloidal calcium carbonate, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; magnesium carbonate, zinc carbonate; organic or inorganic fillers such as carbon black; these fatty acids, resin acids, fatty acid esters For example, a treated product that has been surface-treated with a fatty acid ester urethane compound or the like is used. These may be used alone or in combination of two or more.

  Examples of the plasticizer include polypropylene glycol, diisononyl phthalate (DINP), dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate And methyl acetylricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester; alkylsulfonic acid phenyl ester (for example, mezamol manufactured by Bayer) and the like. These may be used alone or in combination of two or more.

  The pigment may be either an inorganic pigment or an organic pigment. For example, organic pigments such as titanium dioxide, zinc oxide, ultramarine blue, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate inorganic pigment, azo pigment, copper phthalocyanine pigment, and the like can be used.

  The dye is not particularly limited, and conventionally known dyes can be used. For example, a black dye, a yellow dye, a red dye, a blue dye, a brown dye, and the like can be given.

  Examples of the antiaging agent include hindered phenol compounds, hindered amine compounds, benzotriazole compounds, and the like.

  Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

  Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

  Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether, and the like.

  Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, epoxy resins, various silane coupling agents, and the like.

  Examples of the stabilizer include fatty acid silyl esters and fatty acid amide trimethylsilyl compounds.

  The dispersant refers to a substance that makes a solid into fine particles and disperses it in a liquid. Examples thereof include sodium hexametaphosphate, condensed sodium naphthalene sulfonate, and a surfactant.

  The various additives described above can be used in appropriate combination.

  The method for producing the composition according to this embodiment includes, for example, the above-described solvent (A), chlorinated polymer (B), diisocyanate compound (C), silane coupling agent (E) having a mercapto group, and catalyst ( A method of mixing the polyisocyanate compound (D) after sufficiently mixing F) with an agitation device such as a mixer in an inert gas atmosphere such as nitrogen. When the diisocyanate compound (C) contains an aromatic diisocyanate compound or is an aromatic diisocyanate, the above-described solvent (A), chlorinated polymer (B), diisocyanate compound (C) and polyisocyanate are used. A method in which the isocyanate compound (D), the silane coupling agent (E) having a mercapto group, and the catalyst (F) are sufficiently mixed using an agitator such as a mixer in an inert gas atmosphere such as nitrogen. It is done.

  As described above, the composition of the present embodiment includes a solvent (A), a chlorinated polymer (B), a diisocyanate compound (C), a polyisocyanate compound (D), and a silane coupling having a mercapto group. Silane coupling agent (E) and catalyst (F) having a solvent (A), a chlorinated polymer (B), a diisocyanate compound (C), a mercapto group, and an agent (E) and a catalyst (F) And a primer composition obtained by mixing the polyisocyanate compound (D). Thereby, since the diisocyanate compound (C) and the silane coupling agent (E) having a mercapto group can be reacted first, unreacted isocyanate groups in the diisocyanate compound (C) can be reduced. Accordingly, the curing delay can be suppressed at the adhesion interface between the primer and the new sealing material, and the adhesion can be promoted, so that the adhesion can be improved.

  When the diisocyanate compound (C) includes an aromatic diisocyanate compound or is an aromatic diisocyanate, the solvent (A), the chlorinated polymer (B), the diisocyanate compound (C), and the polyisocyanate compound (D), a silane coupling agent (E) having a mercapto group and a catalyst (F) are mixed, and the diisocyanate compound (C) and the silane coupling agent (E) having a mercapto group are given priority first. Since it can be made to react, the delay in curing can be suppressed at the adhesion interface between the primer and the novel sealing material, and the adhesion can be promoted, so that the adhesion can be improved.

  Since the composition of the present embodiment has the excellent characteristics as described above, it is a primer, sealing material, adhesive, etc. for construction, civil engineering, concrete, wood, metal, glass, plastic, etc. It is suitably used for applications.

  Moreover, the composition of this embodiment can be used suitably also as a primer for a hardly-adhesive coating member. Examples of the material of the hardly adhesive coating member that can suitably use the composition of the present embodiment include an acrylic electrodeposition coating member, a fluorine baking coating member, and an anodized coating member. Moreover, the composition of this embodiment can be used also for members other than a hard-to-adhere coating member.

  When used as a primer, examples of adherends include silicone sealing materials, organic polymer (modified silicone) sealing materials having hydrolyzable silicon groups, polyurethane sealing materials, polysulfide sealing materials, and the like. In particular, silicone-based sealing materials, organic polymer sealing materials having hydrolyzable silicon groups, and polyurethane-based sealing materials are preferably used. Among these, an organic polymer sealing material having a hydrolyzable silicon-containing group is preferably used. The organic polymer sealing material having hydrolyzable silicon groups includes a modified silicone sealing material and a two-component modified silicone sealing material. Therefore, according to the composition of the present embodiment, excellent adhesiveness can be obtained even when the sealing material (post-sealing sealing material) is cast and applied.

  The organic polymer having a hydrolyzable silicon-containing group as an adherend when the composition of the present embodiment is used as a primer composition is composed of 1 to 3 hydroxy groups bonded to silicon atoms and hydrolyzable. A silicon-containing group that has one or both of the groups and can be crosslinked by forming a siloxane bond by causing a condensation reaction by using a catalyst or the like, if necessary, in the presence of moisture or a crosslinking agent. is there. When the adherend contains an organic polymer having a hydrolyzable silicon-containing group, curing delays at the adhesion interface between the primer composition of the present embodiment and the organic polymer sealing material having a novel hydrolyzable silicon group. Can be suppressed, adhesion development is fast, and excellent adhesion can be obtained. Examples of the hydrolyzable silicon-containing group include an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidosilyl group, and the like. Specifically, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidosilyl group and the like exemplified by the following formula are preferably used.

  In particular, from the viewpoint of easy handling, the hydrolyzable silicon-containing group is preferably an alkoxysilyl group.

  Further, the alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited, but a methoxy group, an ethoxy group, or a propoxy group is preferable from the viewpoint of easy availability of raw materials.

  The group other than the alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited. For example, a hydrogen atom or an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group An alkenyl group or an arylalkyl group is preferable.

  The number of hydrolyzable silicon-containing groups that the organic polymer having hydrolyzable silicon-containing groups has is at least one per molecule. The bonding position of the hydrolyzable silicon group is preferably at the end of the main chain, and more preferably only at the end of the main chain. Moreover, it is preferable from the point of adhesiveness and a weather resistance to have a hydrolyzable silyl group at both ends of a principal chain, respectively.

  The method for adhering the composition of the present embodiment to an adherend is not particularly limited. For example, the composition of the present embodiment can be applied and immersed in an adherend to be adhered. The composition of the present embodiment is preferably cured under conditions of 5 ° C. or higher and 40 ° C. or lower and 30% RH or higher and 70% RH or lower.

  As mentioned above, although the primer composition of this invention was demonstrated in detail, this invention is not limited to said example, You may perform various change and improvement in the range which does not deviate from the summary of this invention.

  Hereinafter, the composition according to the present embodiment will be specifically described with reference to examples. However, the composition according to the present embodiment is not limited to these.

<Preparation of primer composition (Examples 1 to 8)>
Among the components shown in Table 1, solvent (A), chlorinated polymer (B), diisocyanate compound (C), silane coupling agent (E) having a mercapto group, and catalyst (F) are shown in the same table. After blending in the indicated blending amount (parts by mass) and mixing these uniformly (about 5 hours), the polyisocyanate compound (D) is blended in the blending amount (parts by mass) shown in the table, and further mixed uniformly ( About 1 hour), each primer composition of Examples 1 to 8 shown in Table 1 was prepared. Table 1 shows the amount of each component in each example.

<Preparation of primer composition (Examples 9 to 12, Comparative Examples 1 to 4)>
Each component shown in Table 1 was blended in the blending amount (parts by mass) shown in the same table, and these were uniformly mixed (about 1 hour), and Examples 9 to 12 and Comparative Examples 1 to 4 shown in Table 1 were used. Each primer composition was prepared. Table 1 shows the amount of each component in each Example and Comparative Example.

<Adhesiveness (peel test)>
FIG. 1 is a perspective view showing a state of a peel test. Apply a modified silicone-based sealant 12 (trade name: Super II, manufactured by Yokohama Rubber Co., Ltd.) to a melamine resin-coated super-weather-resistant acrylic electrodeposition coating plate (aluminum plate) 11 and cure at 20 ° C. for 15 hours. After curing, the surface of the sealing material 12 was scraped off with a cutter. Thereafter, each primer composition 13 obtained as described above was applied to the surface of the sealing material 12 that had been scraped off, and allowed to stand at 20 ° C. for 2 minutes, and then a modified silicone-based sealing material 14 (trade name: Super II, Yokohama Rubber Co., Ltd.) Was made under the following curing and curing conditions to obtain a test specimen.
(Curing and curing conditions)
-Adhesion: Cured at 20 ° C for 15 hours and cured at 20 ° C for 30 hours

About each obtained test body, the 90 degree peeling test (peel test) of each primer composition was done by the method shown below, and the adhesion interface was observed visually and evaluated. As shown in FIG. 1, the sealing material 14 was peeled from the adherend 13 in the direction of arrow A so as to be 90 degrees with respect to the adherend 13, and the adhesion was evaluated based on the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
○: The adhesive interface between the primer and the sealing material is cured. ×: The adhesive interface between the primer and the sealing material is uncured.

Each component shown in Table 1 is as follows.
Solvent (A): ethyl acetate, manufactured by Kanto Chemical Co., Ltd. Chlorinated polymer (B): trade name “Pergut S170”, manufactured by Sumika Bayer Urethane Co., Ltd. • Diisocyanate compound (C1): aromatic isocyanate, diphenylmethane diisocyanate (MDI), trade name “Sumijour 44S”, manufactured by Sumitomo Bayer Japan KK • Diisocyanate compound (C2): aromatic isocyanate, tolylene diisocyanate (TDI), trade name “TDI80”, manufactured by Mitsui Chemicals, Inc. • Diisocyanate compound (C3): aliphatic isocyanate, xylene diisocyanate (XDI), trade name “Takenate 500”, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd. • Diisocyanate compound (C4): aliphatic isocyanate, hexamethylene diisocyanate (HDI) , Trade name "Duranate 50M", manufactured by Asahi Kasei Chemicals Co., Ltd.-Polyisocyanate compound (D): TDI-TMP adduct, trade name "Sumidur L-75", NCO group content 13.0% by mass, solid content 65 %, Manufactured by Sumika Bayer Urethane Co., Ltd. ・ Silane coupling agent having a mercapto group (E): γ-mercaptopropyltrimethoxysilane, trade name “KBM-803”, manufactured by Shin-Etsu Chemical Co., Ltd. ・ Catalyst (F): DINP modified tin catalyst, trade name "MSCAT-02", manufactured by Nippon Chemical Industry Co., Ltd.

  From the results shown in Table 1, in Examples 1 to 12, after 15 hours and 30 hours of curing, the adhesion interface between the primer and the sealing material is cured, and both have rapid adhesion and excellent adhesion. Was confirmed.

  On the other hand, in Comparative Examples 1 to 4, the adhesive interface between the primer and the sealing material was cured after curing for 30 hours, but the adhesive interface between the primer and the sealing material was cured after curing for 15 hours. It was uncured, and it was confirmed that the adhesive development was slow and inferior in adhesiveness.

  Therefore, the solvent (A), the chlorinated polymer (B), the diisocyanate compound (C), the silane coupling agent (E) having a mercapto group, and the catalyst (F) are mixed for a predetermined time, and the diisocyanate compound (C) After reacting with the silane coupling agent (E) having a mercapto group, the composition mixed with the polyisocyanate compound (D) is not delayed in curing at the adhesion interface between the primer and the new sealant. In addition, it was confirmed that adhesion development was fast and adhesion could be improved (see Examples 1 to 8).

  When the diisocyanate compound (C) is an aromatic isocyanate, the solvent (A), the chlorinated polymer (B), the diisocyanate compound (C), the polyisocyanate compound (D), and a silane coupling agent having a mercapto group ( E) and catalyst (F) are mixed, and the diisocyanate compound (C) and the silane coupling agent (E) having a mercapto group are preferentially reacted, whereby the adhesion interface between the primer and the new sealing material Thus, it was confirmed that the adhesive development was quick and the adhesiveness could be improved without causing curing delay (see Examples 9 to 12).

  Therefore, the diisocyanate compound includes a solvent (A), a chlorinated polymer (B), a diisocyanate compound (C), a polyisocyanate compound (D), a silane coupling agent (E) having a mercapto group, and a catalyst (F). The primer composition in which (C) and the silane coupling agent (E) having a mercapto group are preferentially reacted is compared with the conventional primer composition at the adhesive interface between the primer composition and the new sealing material. It has been found that it can be suitably used as a primer composition used when succeeding a sealing material because it can suppress curing delay, promote adhesion development, and is excellent in adhesiveness.

11 Adhering body 12 Sealing material 13 Primer composition 14 Sealing material

Claims (6)

Solvent (A),
A chlorinated polymer (B);
A diisocyanate compound (C);
A polyisocyanate compound (D);
A silane coupling agent (E) having a mercapto group;
A catalyst (F),
Including
After mixing the solvent (A), the chlorinated polymer (B), the diisocyanate compound (C), the silane coupling agent (E) having the mercapto group, and the catalyst (F), the polyisocyanate compound. A primer composition obtained by mixing (D). Solvent (A),
A chlorinated polymer (B);
A diisocyanate compound (C);
A polyisocyanate compound (D);
A silane coupling agent (E) having a mercapto group;
A catalyst (F),
Including
The primer composition, wherein the diisocyanate compound (C) is an aromatic diisocyanate compound.   The primer composition according to claim 1 or 2, wherein the catalyst (F) is a tin-based catalyst.   The primer composition according to any one of claims 1 to 3, which is used for a two-component modified silicone sealant.   The primer composition according to any one of claims 1 to 4, which is used for joining a sealing material and a sealing material.   The primer composition according to claim 4 or 5, wherein the sealing material contains an organic polymer having a hydrolyzable silicon-containing group.

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