JP2013001835A - Primer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer composition having low viscosity and excellent workability with excellent operatability and safety and further having excellent adhesion improvement.SOLUTION: The primer composition is obtained containing an isocyanate group-containing compound and a solvent and having no ignition point observed by a method designated by: the appended table 1 and note 10 in a supplementary provision in the Fire Service Law; the paragraph 6 of Article 1 in Ministerial ordinance concerning the test and the property of a dangerous object; and the appended tables 9 and 10 in the Ministerial ordinance concerning the test and the property of a dangerous object. The primer composition has excellent operability and safety because the ignition point is not observed and has low viscosity and excellent workability. Further, the primer composition is excellent in adhesion improvement.

Description

  The present invention relates to a primer composition, and more particularly to a primer composition that is treated between a substrate and an adherend.

  Conventionally, in order to improve the adhesion between a base material and an adherend, it is known that the base material is pretreated with a primer composition. Various primer compositions are known.

  Specific examples of the urethane primer composition include, for example, an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate containing tolylene diisocyanate and a polyoxyalkylene polyol, xylene, toluene, ethyl acetate, butyl acetate, and the like. Has been proposed (see, for example, Patent Document 1).

JP 2002-3781 A

  However, since the urethane primer composition such as the fast curable primer composition for urethane coating waterproofing material described in Patent Document 1 usually contains the above-mentioned organic solvent, it may cause ignition due to the construction environment or the like. There are problems such as poor handling and safety.

  In general, the primer composition is required to have a low viscosity from the viewpoint of workability at the time of processing, and further, it is required to ensure better adhesive strength improvement. .

  Accordingly, an object of the present invention is to provide a primer composition that is excellent in handleability and safety, is low in viscosity and excellent in workability, and is also excellent in improvement in adhesion.

  In order to achieve the above-mentioned object, the primer composition of the present invention contains an isocyanate group-containing compound and a solvent, and the Fire Service Act (Act No. 186 of July 24, 1947) Supplementary Provisions (Act No. 34 of May 1, 2000) Appendix 1 Remarks 10, Decree on the Regulation of Dangerous Goods (Cabinet Order No. 306 on September 26, 1944) Article 1 No. 6 (Class 4 Dangerous Goods Test), Dangerous Goods Test and Property Decree (Ministry of Autonomy Ordinance No. 1 of February 17, 1989), flammable by the methods specified in Schedules 9 and 10 It is characterized by the fact that no dots are observed.

  In the primer composition of the present invention, it is preferable that the solvent contains 1-bromopropane.

  Moreover, in the primer composition of this invention, it is suitable that the content rate of the said solvent is 30-80 mass%.

  The primer composition of the present invention is supplementary to the Fire Service Act (Act No. 186 of July 24, 1947) Supplementary Schedule (Act No. 34 of May 1, 2000), Appendix 1 Remarks 10. Decree on dangerous goods regulations (December 26, 1964, Decree No. 306) Article 1-6 (Class 4 Dangerous Goods Test), Dangerous Goods Test and Properties The flash point is not observed by the method specified in the Ministerial Ordinance (Ministry of Autonomy Ordinance No. 1 of February 17, 1989) Attached Tables 9 and 10, which makes it easy to handle and safe.

  Moreover, since the primer composition of the present invention has a low viscosity, it is excellent in workability and further excellent in adhesive strength improvement.

  The primer composition of the present invention contains an isocyanate group-containing compound and a solvent.

  As an isocyanate group containing compound, a monoisocyanate compound and a polyisocyanate compound are mentioned, for example.

  The monoisocyanate compound is an organic compound containing one isocyanate group, and examples thereof include methyl isocyanate, ethyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate, phenyl isocyanate, and benzyl isocyanate.

  These monoisocyanate compounds can be used alone or in combination of two or more.

  The polyisocyanate compound is an organic compound containing two or more isocyanate groups, and examples thereof include polyisocyanate monomers, polyisocyanate derivatives, and isocyanate group-terminated prepolymers.

  Examples of the polyisocyanate monomer include aromatic polyisocyanate, araliphatic polyisocyanate, and aliphatic polyisocyanate.

  Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4, 4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), Examples include aromatic diisocyanates such as 4,4′-toluidine diisocyanate (TODI) and 4,4′-diphenyl ether diisocyanate.

  Examples of the araliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra). Methyl xylylene diisocyanate or a mixture thereof (TMXDI), aromatic aliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene, and the like.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 , 5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capate Group diisocyanate and the like.

Aliphatic polyisocyanates include alicyclic polyisocyanates. Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis (cyclohexylisocyanate, these Trans, Trans - body, Trans, Cis body, Cis, Cis body, or mixtures _thereof)) (H 12 _MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane Isocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane Or a mixture thereof) (H ₆ XDI) and the like.

  These polyisocyanate monomers can be used alone or in combination of two or more.

  Examples of the polyisocyanate derivative include a multimer (for example, dimer, trimer (for example, isocyanurate-modified product, iminooxadiazinedione-modified product), pentamer, 7) of the polyisocyanate monomer described above. Etc.), allophanate-modified products (for example, allophanate-modified products produced from the reaction of the above-mentioned polyisocyanate monomer and low molecular weight polyol), polyol modified products (for example, polyisocyanate monomer and low molecular weight polyol) Polyol-modified products (alcohol adducts, etc.) produced by the reaction with benzene, biuret-modified products (for example, biuret-modified products produced by the reaction of the above-mentioned polyisocyanate monomers with water and amines, etc.), urea modification Body (for example, produced by reaction of polyisocyanate monomer and diamine as described above) Modified oxadiazine trione (for example, oxadiazine trione produced by the reaction of the above polyisocyanate monomer and carbon dioxide), carbodiimide modified (such as the above polyisocyanate monomer) Carbodiimide-modified products produced by the decarboxylation condensation reaction), uretdione-modified products, uretonimine-modified products, and the like.

  The low molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of less than 300, preferably less than 400, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethyl Pentanediol, 3,3-dimethylolheptane, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and their Mixture, hydrogenated bisphenol A, 1,4-dihydroxy- -Dihydric alcohols such as butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, such as glycerin, trimethylolpropane, triisopropanolamine Trihydric alcohols such as tetramethylolmethane (pentaerythritol), tetrahydric alcohols such as diglycerin, pentavalent alcohols such as xylitol, such as sorbitol, mannitol, allitol, iditol, dulitol, altritol, inositol, dipentol Examples include hexavalent alcohols such as erythritol, for example, 7-valent alcohols such as perseitol, and 8-valent alcohols such as sucrose.

  These low molecular weight polyols can be used alone or in combination of two or more.

  Furthermore, examples of the polyisocyanate derivative include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI, polynuclear-containing diphenylmethane diisocyanate) and the like.

  These polyisocyanate derivatives can be used alone or in combination of two or more.

  The isocyanate group-terminated prepolymer is a urethane prepolymer having at least two isocyanate groups at the molecular ends, and is a polyisocyanate (polyisocyanate selected from polyisocyanate monomers, polyisocyanate derivatives and isocyanate group-terminated prepolymers, preferably A polyisocyanate selected from a polyisocyanate monomer and a polyisocyanate derivative), a high molecular weight polyol (and optionally a low molecular weight polyol), and a polyisocyanate for the hydroxyl group of the high molecular weight polyol (and optionally a low molecular weight polyol). The equivalent ratio (NCO / OH) can be obtained by a urethanization reaction at a ratio of greater than 1, preferably 1.5 to 50.

  The high molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 300 or more, preferably 400 or more. For example, polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin Examples include polyols, acrylic polyols, and vinyl monomer-modified polyols.

  Examples of the polyether polyol include polyoxyalkylene polyols such as polypropylene polyol (polyoxypropylene polyol) and polytetramethylene ether polyol.

  Examples of the polypropylene polyol include, for example, the above-described low molecular weight polyols and the like, addition polymers of propylene oxide starting from aromatic polyamines, aliphatic polyamines, and the like (random and / or propylene oxide and alkylene oxides such as ethylene oxide). Or a block copolymer).

  Examples of the polytetramethylene ether polyol include a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran, and an amorphous polytetramethylene ether glycol obtained by copolymerizing the above dihydric alcohol with a polymerization unit such as tetrahydrofuran or methyltetrahydrofuran. Etc.

  Examples of the polyester polyol include polycondensates obtained by reacting the above-described low molecular weight polyol and polybasic acid under known conditions.

  Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , Azelaic acid, sebacic acid, other saturated aliphatic dicarboxylic acids (C11-13) such as maleic acid, fumaric acid, itaconic acid, other unsaturated aliphatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid , Toluene dicarboxylic acid, naphthalene dicarboxylic acid, other aromatic dicarboxylic acids such as hexahydrophthalic acid, other alicyclic dicarboxylic acids such as dimer acid, hydrogenated dimer acid, het acid and other carboxylic acids, And acid anhydrides derived from these carboxylic acids, such as oxalic anhydride, succinic anhydride , Maleic anhydride, phthalic anhydride, 2-alkyl (C12-C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and acid halides derived from these carboxylic acids, such as oxalic acid Examples include dichloride, adipic acid dichloride, and sebacic acid dichloride.

  Further, as the polyester polyol, for example, a plant-derived polyester polyol, specifically, a hydroxyl group-containing vegetable oil fatty acid (for example, castor oil fatty acid containing ricinoleic acid, 12-hydroxystearic acid, using the above-described low molecular weight polyol as an initiator, And vegetable oil-based polyester polyols obtained by subjecting a hydroxycarboxylic acid such as hydrogenated castor oil fatty acid and the like to a condensation reaction under known conditions.

  Further, as the polyester polyol, for example, the above-described low molecular weight polyol (preferably dihydric alcohol) is used as an initiator, for example, lactones such as ε-caprolactone and γ-valerolactone, for example, L-lactide, D- Examples thereof include polycaprolactone polyol, polyvalerolactone polyol obtained by ring-opening polymerization of lactides such as lactide, and lactone polyester polyol obtained by copolymerizing the above-described dihydric alcohol.

  As the polycarbonate polyol, for example, a ring-opening polymer of ethylene carbonate using the above-described low molecular weight polyol (preferably a dihydric alcohol) as an initiator, for example, 1,4-butanediol, 1,5-pentanediol, Examples thereof include amorphous polycarbonate polyols obtained by copolymerizing a dihydric alcohol such as 3-methyl-1,5-pentanediol or 1,6-hexanediol with a ring-opening polymer.

  Further, the polyurethane polyol is a ratio in which the equivalent ratio (OH / NCO) of the hydroxyl group (OH) to the isocyanate group (NCO) of the polyester polyol, polyether polyol and / or polycarbonate polyol obtained as described above exceeds 1, By reacting with polyisocyanate, it can be obtained as polyester polyurethane polyol, polyether polyurethane polyol, polycarbonate polyurethane polyol, or polyester polyether polyurethane polyol.

  Examples of the epoxy polyol include an epoxy polyol obtained by a reaction of the above-described low molecular weight polyol with a polyfunctional halohydrin such as epichlorohydrin or β-methylepichlorohydrin.

  Examples of the vegetable oil polyol include hydroxyl group-containing vegetable oils such as castor oil and coconut oil. For example, castor oil polyol, or ester-modified castor oil polyol obtained by reaction of castor oil fatty acid and polypropylene polyol can be used.

  Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.

  Examples of the acrylic polyol include a copolymer obtained by copolymerizing a hydroxyl group-containing acrylate and a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylate.

  Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, polyhydroxyalkyl maleate, Examples thereof include polyhydroxyalkyl fumarate. Preferably, 2-hydroxyethyl (meth) acrylate etc. are mentioned.

  Examples of the copolymerizable vinyl monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and s-butyl ( Alkyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl acrylate, and the like ( (Meth) acrylate (C1-C12), for example, aromatic vinyl such as styrene, vinyltoluene, α-methylstyrene, for example, vinyl cyanide such as (meth) acrylonitrile, for example, ( A) Vinyl monomers containing a carboxyl group such as acrylic acid, fumaric acid, maleic acid, itaconic acid, or alkyl esters thereof such as ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di ( Alkane polyol poly (meth) acrylates such as meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, for example 3- (2-isocyanate-2 And vinyl monomers containing isocyanate groups such as -propyl) -α-methylstyrene.

  The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylate and copolymerizable vinyl monomer in the presence of a suitable solvent and polymerization initiator.

  The acrylic polyol includes, for example, silicone polyol and fluorine polyol.

  Examples of the silicone polyol include an acrylic polyol in which a silicone compound containing a vinyl group such as γ-methacryloxypropyltrimethoxysilane is blended as the copolymerizable vinyl monomer in the copolymerization of the acrylic polyol described above. .

  As the fluorine polyol, for example, in the copolymerization of the acrylic polyol described above, as the copolymerizable vinyl monomer, for example, an acrylic polyol in which a fluorine compound containing a vinyl group such as tetrafluoroethylene or chlorotrifluoroethylene is blended may be mentioned. .

  The vinyl monomer-modified polyol can be obtained by a reaction between the above-described high molecular weight polyol and a vinyl monomer.

  These high molecular weight polyols can be used alone or in combination of two or more.

  The urethanization reaction can be based on a known method. The reaction temperature in the urethanization reaction is, for example, 50 to 120 ° C., preferably 50 to 100 ° C., and the reaction time is, for example, 0.5 to 15 hours, preferably 1 to 10 hours.

  In the urethanization reaction, if necessary, an organic solvent is blended, and in the presence thereof, an isocyanate group-terminated prepolymer can be prepared (solution polymerization).

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; nitriles such as acetonitrile; alkyl esters such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate; Aliphatic hydrocarbons such as hexane, n-heptane, and octane, for example, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, such as methyl cellosolve acetate , Ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxy Glycol ether esters such as butyl acetate and ethyl-3-ethoxypropionate, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, iodine Halogenated aliphatic hydrocarbons such as methylene chloride and dichloroethane, for example, polar aprotics such as N-methylpyrrolidone, dimethylformamide, N, N′-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, and the like And non-flammable solvents.

  These organic solvents can be used alone or in combination of two or more.

  The organic solvent is preferably a non-flammable solvent.

  In solution polymerization, if a non-flammable solvent is used as the organic solvent, the non-flammable solvent can be used as it is as a solvent described later.

  In solution polymerization, the blending ratio of the organic solvent is appropriately set depending on the purpose and application.

  Moreover, in the said urethanation reaction, well-known urethanation catalysts, such as amines and an organometallic compound, can be added as needed.

  Examples of the amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, such as imidazole, Examples thereof include imidazoles such as 2-ethyl-4-methylimidazole.

  Examples of organometallic compounds include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin Organic tin compounds such as dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dibutyltin dichloride, for example, organic lead compounds such as lead octoate and lead naphthenate, for example, organic nickel compounds such as nickel naphthenate, for example And organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octenoate, and organic bismuth compounds such as bismuth octylate and bismuth neodecanoate.

  Furthermore, examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.

  These urethanization catalysts can be used alone or in combination of two or more.

  As the urethanization catalyst, an organometallic compound is preferable, and an organotin compound is more preferable.

  Furthermore, if necessary, free (unreacted) polyisocyanate may be removed from the resulting isocyanate group-terminated prepolymer by a known removal means such as distillation or extraction.

  Moreover, when preparing an isocyanate group terminal prepolymer by solution polymerization, when using an organic solvent, these organic solvents are removed by the above-mentioned well-known removal means as needed. In particular, when an organic solvent other than the non-flammable solvent is used, the organic solvent other than the non-flammable solvent is preferably removed by the known removal means described above.

  The isocyanate group equivalent of the isocyanate group-terminated prepolymer (solid content) is, for example, 85 to 2200, preferably 150 to 1500. Moreover, content of the unreacted polyisocyanate in isocyanate group terminal prepolymer (solid content) is 100 mass% or less, for example, Preferably, it is 95 mass% or less, More preferably, it is 90 mass% or less.

  In addition, an isocyanate group equivalent is synonymous with an amine equivalent, and can be calculated | required by A method or B method of JISK1603-1 (2007). The content of unreacted polyisocyanate can be determined, for example, by HPLC measurement.

  And the isocyanate group content (isocyanate group content, NCO%) of such an isocyanate group-terminated prepolymer (solid content) is, for example, 2 to 50% by mass, preferably 2.8 to 28% by mass, Preferably, it is 3-25 mass%, and the average functional group number of an isocyanate group is 1.2-5.0, for example, Preferably, it is 1.5-4.5.

  These polyisocyanate compounds can be used alone or in combination of two or more.

  These isocyanate group-containing compounds can be used alone or in combination of two or more.

  The isocyanate group-containing compound is preferably a polyisocyanate compound, more preferably an isocyanate group-terminated prepolymer.

  For solvents, the Fire Service Act (Act No. 186 of July 24, 1947) Supplementary Schedule (Act No. 34 of May 1, 2000) Appendix 1 Remarks 10, Dangerous Goods Decree (No. 306 of Sept. 26, 1964) on Article 1 of the Regulations, Article 1-6 (Class 4 Dangerous Goods Testing), Ministerial Ordinance on Dangerous Goods Testing and Properties (Heisei 1 February 17, 2005, Ministry of Home Affairs Ordinance No. 1) Solvents whose flash point is not observed (non-flammable solvents) are used by the methods prescribed in Schedules 9 and 10, and as such non-flammable solvents, Specific examples include 1-bromopropane, 1,1,1-trichloroethane, trichloroethylene, methylene chloride, dichloropentafluoropropane, and the like.

  These non-flammable solvents can be used alone or in combination of two or more.

  As a solvent, Preferably, 1-bromopropane is mentioned.

  When 1-bromopropane is used, it is possible to reduce the viscosity of the primer composition, and to ensure excellent adhesion improvement.

  Such a solvent can be obtained as a commercial product. Examples of such a commercial product include “Absol JG” manufactured by Albemarle, “n-propyl bromide” manufactured by Manac, “n-propyl bromide” manufactured by Tosoh Organic Chemical Co., Ltd. Propyl bromide "(all are 1-bromopropane) and the like.

  Such a solvent can be directly blended and mixed with, for example, an isocyanate group-containing compound. For example, when an isocyanate group-terminated prepolymer prepared by solution polymerization is used as the isocyanate group-containing compound, The solvent used in the solution polymerization can be used as it is.

  In the primer composition, the content (solid content concentration) of the isocyanate group-containing compound is, for example, 10 to 90% by mass, preferably 20 to 70% by mass, more preferably 25%, based on the total amount of the primer composition. It is -70 mass%, and the content rate of a solvent is 10-90 mass% with respect to the total amount of a primer composition, Preferably, it is 30-80 mass%, 30-75 mass%.

  If the content rate of a solvent is the said range, the viscosity of a primer composition will be adjusted and, thereby, the primer composition which is excellent in the workability | operativity at the time of a process can be obtained.

  The viscosity (based on JIS K7117-1 (1995)) at 25 ° C. of the primer composition is, for example, 1 to 1000 mPa · s, and preferably 2 to 800 mPa · s.

  If the viscosity of a primer composition is the said range, a primer composition can be processed with sufficient workability | operativity.

  Moreover, the isocyanate group content rate (NCO%) (based on JIS K7301 (1995)) of such a primer composition is 0.2-45 mass%, for example, Preferably, it is 0.3-25 mass% is there.

  And such primer composition is attached to the Fire Service Act (Act No. 186 of July 24, 1947) Supplementary Schedule (Act No. 34 of May 1, 2000) (1) Remarks 10, Cabinet Order on Dangerous Goods Regulations (Cabinet Order No. 306, September 26, 1944) Article 1-6 (Class 4 Dangerous Goods Test), Dangerous Goods Test and The flash point is not observed according to the methods specified in Schedules 9 and 10 of the Ministerial Ordinance on Properties (Ministry of Autonomy Ordinance No. 1 of February 17, 1989).

  Specifically, the primer composition is a JIS K2265 (1980) “crude oil and crude oil” designated in Schedule 9 of the Ministerial Ordinance on the Testing and Properties of Dangerous Goods (Ministerial Ordinance No. 1 of February 17, 1989). Petroleum product flash point test method ”The flash point is not measured at 80 ° C or lower by the method of Appendix 9 using the tag sealed flash point tester specified in 4.2.2. Cleveland specified in JIS K2265 (1980) "Crude oil and petroleum products flash point test method" specified in Schedule 10 of the Ministerial Ordinance on Decree (Ministry of Autonomy Ordinance No. 1 of February 17, 1989) The flash point is not measured by the method shown in Table 10 using an open flash point tester.

  And such primer composition is attached to the Fire Service Act (Act No. 186 of July 24, 1947) Supplementary Schedule (Act No. 34 of May 1, 2000) (1) Remarks 10, Cabinet Order on Dangerous Goods Regulations (Cabinet Order No. 306, September 26, 1944) Article 1-6 (Class 4 Dangerous Goods Test), Dangerous Goods Test and Since the flash point is not observed by the method specified in Appendices 9 and 10 of the Ministry Ordinance on Properties (February 17, 1989, Ministry of Autonomy Ordinance No. 1), it is excellent in handling and safety.

  Moreover, such a primer composition is excellent in workability because of its low viscosity, and further, is excellent in adhesive strength improvement.

  Therefore, such a primer composition can be used in various industrial fields as a primer composition that is treated in order to improve the adhesion between the substrate and the adherend.

  Specifically, such a primer composition is, for example, an industrial primer composition treated between a plastic substrate and a coating layer laminated on the plastic substrate, for example, slate (rock) It can be suitably used as a building primer composition or the like that is processed between a base material such as concrete and a paving material such as a ground material applied on the base material.

  In addition, it does not restrict | limit especially as a processing method of a primer composition, A well-known method is employable. Specifically, first, a primer composition is applied on a substrate, cured to an extent that surface tack is eliminated (for example, moisture curing), and then applied to the substrate via the primer composition. Laminate the body. In such a case, the application amount of the primer composition is not particularly limited, and is appropriately set according to the purpose and application.

  Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited by the following Example.

Example 1 (Synthesis of primer composition a)
Takenate 500 (trade name, 1,3-xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc.) 395 under a nitrogen atmosphere in a 1-liter four-necked flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube 0.1 g, Actol MN-450 (trade name, polypropylene polyol having an average molecular weight of about 375, manufactured by Mitsui Chemicals), 104.8 g, 0.1 g of dibutyltin dilaurate, and Absol JG (trade name, 1-bromopropane) , Made by Albemarle Co., Ltd.) and urethanized at 65 ° C. for 3 hours. The reaction was stopped when NCO% reached 14.1% by mass to obtain primer composition a.

  The obtained primer composition a showed a uniform appearance, its viscosity at 25 ° C. was 4 mPa · s, and its flash point was not detected.

  NCO% was measured by an isocyanate group content test described in JIS K7301. The viscosity was measured by the method described in JIS K7117. In addition, the flash point is in accordance with the Fire Service Act (Act No. 186 of July 24, 1947) Supplementary Schedule (Act No. 34 of May 1, 2000) Appendix 1 Remarks 10, Ministerial Ordinance on the Regulation of Dangerous Goods (Decree No. 306 of September 26, 1944) Article 1-6 (Test for Dangerous Goods of Class 4), Dangerous Goods Examination and Properties February 17, 1989 (Ministry of Home Affairs Ordinance No. 1) Observed by the methods specified in Schedules 9 and 10 (the same shall apply hereinafter).

Example 2 (Synthesis of primer composition b)
Cosmonate M200 (trade name, polymethylene polyphenyl polyisocyanate, manufactured by Mitsui Chemicals, Inc.) 406 was added to a 1-liter four-necked flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube under a nitrogen atmosphere. 0.5 g, 93.5 g of Actol MN-450, and 500.0 g of Absol JG were charged and urethanized at 65 ° C. for 3 hours. The reaction was stopped when NCO% reached 9.5% by mass to obtain primer composition b.

  The obtained primer composition b showed a uniform appearance, its viscosity at 25 ° C. was 20 mPa · s, and its flash point was not detected.

Example 3 (Synthesis of primer composition c)
Urethane reaction until NCO% reaches 8.5% by mass, as in Example 1, except that Takenate 500 is 237.0 g, Actol MN-450 is 62.9 g, and Absol JG is 700.0 g. To obtain a primer composition c.

  The obtained primer composition c showed a uniform appearance, had a viscosity at 25 ° C. of 3 mPa · s and a flash point of not detected.

Example 4 (Synthesis of primer composition d)
The urethanization reaction was carried out until NCO% reached 5.6% by mass, as in Example 2, except that 243.9 g of Cosmonate M200, 56.1 g of Actol MN-450, and 700 g of Absol JG were used. A primer composition d was obtained.

  The obtained primer composition d showed a uniform appearance, had a viscosity at 25 ° C. of 7 mPa · s and a flash point of not detected.

Example 5 (Synthesis of primer composition e)
Urethane reaction until NCO% reaches 18.4% by mass, as in Example 1, except that 513.7 g of Takenate 500, 136.2 g of Actol MN-450, and 350.0 g of Absol JG. To obtain a primer composition e.

  The obtained primer composition e showed a uniform appearance, its viscosity at 25 ° C. was 8 mPa · s, and its flash point was not detected.

Example 6 (Synthesis of primer composition f)
A urethanization reaction was carried out until NCO% reached 14.3% by mass, as in Example 2, except that 543.3 g of Cosmonate M200, 106.7 g of Actol MN-450, and 350 g of Absol JG were used. The primer composition f was obtained.

  The obtained primer composition f showed a uniform appearance, its viscosity at 25 ° C. was 25 mPa · s, and its flash point was not detected.

Comparative Example 1 (Synthesis of primer composition g)
A primer composition g was obtained in the same manner as in Example 1 except that ethyl acetate was used instead of Absol JG until NCO% reached 14.1% by mass.

  The obtained primer composition g showed a uniform appearance, its viscosity at 25 ° C. was 3 mPa · s, and its flash point was −2 ° C.

Comparative Example 2 (Synthesis of primer composition h)
A primer composition h was obtained in the same manner as in Example 2 except that ethyl acetate was used instead of Absol JG until NCO% reached 9.5% by mass.

  The obtained primer composition h showed a uniform appearance, its viscosity at 25 ° C. was 16 mPa · s, and its flash point was −3 ° C.

  Table 1 shows the solvents contained in the primer compositions obtained in each Example and each Comparative Example, and the physical properties of the primer compositions.

評価
各実施例のプライマー組成物は、消防法（昭和二十三年七月二十四日法律第百八十六号）付則（平成二一年五月一日法律第三四号）別表第一 備考十、危険物の規則に関する政令（昭和三十四年九月二十六日政令第三百六号）第一条の六（第四類の危険物の試験）、危険物の試験及び性状に関する省令（平成元年二月十七日自治省令第一号）別表第九および第十に規定された方法により、引火点が観測されなかったのに対し、各比較例のプライマー組成物は、引火点が観測され、また、その値は、消防法上の危険物第４類第一石油類（１気圧において引火点が２１℃未満）に相当した。

Evaluation The primer composition of each example is shown in the appendix of the Fire Service Act (Act No. 186 of July 24, 1947), Supplementary Schedule (Act No. 3 of May 1, 2000) (1) Remarks 10, Cabinet Order on Dangerous Goods Regulations (Cabinet Order No. 306, September 26, 1944) Article 1-6 (Class 4 Dangerous Goods Test), Dangerous Goods Test and While the flash point was not observed by the methods specified in Appendices 9 and 10 of the Ministerial Ordinance on Properties (February 17, 1989, Ministry of Self-Government Ordinance No. 1), the primer composition of each comparative example was The flash point was observed, and the value thereof corresponded to the Class 4 No. 1 petroleum (having a flash point of less than 21 ° C. at 1 atm) under the Fire Service Act.

  Moreover, it was confirmed that the primer composition of each Example has a low viscosity at 25 ° C.

Usage examples 1-4
A slate plate (product number flexible sheet N, manufactured by Nozawa) having a thickness of 5 mm was prepared as a base material.

Next, the primer compositions a, b, g, and h obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were applied to the slate plate with a brush so that the coating amount was 150 g / m ² , respectively. The solution was allowed to stand at 23 ° C. under a relative humidity of 55% for 1 hour and dried.

  After 1 hour, after confirming dryness by touch, a urethane ground material (product number Hyprene P-306 / TSR-82M, manufactured by Mitsui Chemicals, Inc.) was used as an adherend (adhesion layer) on the primer composition. ) Was applied to a thickness of 2 mm and cured for 7 days at 23 ° C. and 55% relative humidity to produce a sample.

  The obtained sample was cut to a width of 15 mm, and subjected to a 180 ° peel test at a crosshead speed of 50 mm / min using a universal tension measuring device (Orientec Co., Ltd.) at 25 ° C. and a relative humidity of 55% to determine the adhesive strength. The adhesion was evaluated by observing the peeled state. The results are shown in Table 2.

なお、表２において、指触による乾燥の確認においてタック性が確認されなかった場合、指触乾燥性を「良好」とする。

In Table 2, when the tackiness is not confirmed in the confirmation of drying by touching the finger, the touch drying property is set to “good”.

  Further, “100% adherent layer destruction” means that the base material and the primer composition are not destroyed while the base material, the primer composition and the adherent layer (parts in contact with the primer composition) are adhered. It shows a state in which only the adherent layer has been destroyed, thereby indicating that the substrate and the adherent layer are well bonded.

Claims (3)

Containing an isocyanate group-containing compound and a solvent,
Supplementary Provisions (Act No. 86 of May 1, 2000) of the Fire Services Act (Act No. 186 of July 24, 1947) Appendix 1 Remarks 10, Decree on the Regulation of Dangerous Goods (Decree No. 306 of September 26, 1954) Article 1-6 (Class 4 Dangerous Goods Test), Ministerial Ordinance on Dangerous Goods Testing and Properties (February 10, 1989) 7th Ministry of Home Affairs Ordinance No. 1) A primer composition characterized in that a flash point is not observed by the methods specified in Appended Tables 9 and 10.   The primer composition according to claim 1, wherein the solvent contains 1-bromopropane.   The primer composition according to claim 1 or 2, wherein the content of the solvent is 30 to 80% by mass.