WO2014136800A1 - 一液湿気硬化型組成物 - Google Patents
一液湿気硬化型組成物 Download PDFInfo
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- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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Definitions
- the present invention relates to a one-component moisture-curable composition.
- Urethane resin compositions utilizing moisture curing are widely used in various fields such as the automotive field and the architectural field.
- a primer composition is previously applied to the bonding surface, and then an adhesive is applied thereon to attach the window glass to the vehicle body.
- Patent Document 1 discloses a primer by adding an appropriate amount of an aliphatic hydrocarbon compound such as polybutene or polyisobutene, which is a compound having an isocyanate group-terminated urethane prepolymer as a main component and a solubility parameter value of 6.0 or more and 9.0 or less.
- an aliphatic hydrocarbon compound such as polybutene or polyisobutene
- a one-component moisture-curable urethane composition that can be adhered to a coated steel sheet without using a coating is described.
- Patent Document 2 discloses a preliminary composition composed of a urethane prepolymer, a filler and a plasticizer, a specific adhesion-imparting agent, dimorpholinodiethyl ether, N, N-dimethylaminoethylmorpholine, One-part moisture curing that can adhere to difficult-to-adhere coated steel sheets without using a primer by making the specific relationship between the content of 2-methyl-1,4-diazabicyclo [2,2,2] octane and organotin compounds A type urethane composition is described.
- adhesive compositions for automobiles are bonded at high temperature and high humidity while adhering a glass adherend without applying a primer to a difficult adherend such as a painted adherend. It is required that properties such as property, curing speed, drooping property, storage stability, heat resistant adhesiveness and elongation at break can be satisfied.
- the one-component moisture-curable urethane composition described in Patent Documents 1 and 2 adheres a glass adherend without performing a ground treatment on a difficult-to-adhere adherend such as a painted adherend. There is room for improvement in order to be able to satisfy characteristics such as drooping property, heat-resistant adhesiveness and elongation at break.
- the present invention is a one-component solution that has excellent adhesion without subjecting a coated adherend to ground treatment, and can also satisfy characteristics such as drooping, heat-resistant adhesion, and elongation at break.
- An object is to provide a moisture curable composition.
- the present invention includes the following (1) to (4).
- a preliminary composition comprising a urethane prepolymer having an isocyanate group at the terminal and carbon black;
- a compound (A) obtained by reacting diisocyanate with trimethylolpropane or glycerin so that the equivalent ratio of isocyanate group to hydroxyl group is 1.8 or more and 2.2 or less, and a diisocyanate burette or isocyanurate
- An adhesion-imparting agent comprising any one or both of a certain compound (B);
- Compound (C) obtained by reacting 1,3-diacetoxy-1,1,3,3-tetrabutyldistanoxane and ethyl silicate in a molar ratio of 1: 0.8 to 1: 1.2
- a first catalyst containing either or both of dibutyltin bis (pentadione),
- a second catalyst comprising dimorpholinodiethyl ether;
- the second catalyst further contains N, N-dimethylaminoethylmorpholine,
- the one-component moisture-curing type according to the above (1) that satisfies the following formula (4) with respect to 100 parts by mass of the preliminary composition Composition.
- F ⁇ 2 (4) (3) The one-component moisture-curable composition according to the above (1) or (2) that satisfies the following formulas (5) and (6) with respect to 100 parts by mass of the preliminary composition.
- F ⁇ E (5) 0.1 ⁇ (E + F) ⁇ 2 (6) (4) The one-component moisture-curable composition according to any one of (1) to (3), wherein the diisocyanate is hexamethylene diisocyanate.
- the coated adherend is provided with excellent adhesion without performing a ground treatment, and characteristics such as drooping property, heat-resistant adhesion, and elongation at break can also be satisfied.
- FIG. 1 is a conceptual diagram illustrating an example of a drooping test.
- the one-component moisture-curable composition according to the present embodiment includes a preliminary composition, an adhesion-imparting agent, a first catalyst, and a second catalyst. Yes.
- the preliminary composition contains a urethane prepolymer having an isocyanate group at the terminal and carbon black.
- the urethane prepolymer is a prepolymer containing a plurality of isocyanate groups in the molecule at the molecular ends.
- the urethane prepolymer is preferably liquid at room temperature from the viewpoint of handling.
- the method for producing the urethane prepolymer is not particularly limited, and conventionally known methods can be mentioned.
- the urethane prepolymer is, for example, a reaction product obtained by reacting a polyisocyanate compound and a polyol compound so that isocyanate groups (NCO groups) are excessive with respect to hydroxy groups (OH groups).
- the urethane prepolymer generally contains 0.5% by mass or more and 10% by mass or less of NCO groups at the molecular ends. This isocyanate group may be bonded to either an aromatic hydrocarbon or an aliphatic hydrocarbon.
- the polyisocyanate compound used when producing the urethane prepolymer is not particularly limited as long as it has two or more isocyanate groups in the molecule.
- examples of the polyisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate (4,4 ′).
- Aromatic polyisocyanates such as diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), triphenylmethane triisocyanate; Aliphatic polyisocyanates such as diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI),
- 4,4′-MDI is preferably used as the polyisocyanate compound used when synthesizing the urethane prepolymer used in the present embodiment from the viewpoint of easy availability and low cost. .
- the polyol compound used when producing the urethane prepolymer is not particularly limited, and may be, for example, any of polyether polyol, polyester polyol, acrylic polyol, polycarbonate polyol, and other polyols. These polyols can be used alone or in combination of two or more.
- polyol compound examples include polypropylene ether diol, polyethylene ether diol, polypropylene ether triol, polytetramethylene glycol, polyethylene glycol (PEG), polypropylene glycol (PPG), polyoxyethylene glycol, polyoxypropylene glycol, polyoxy Propylene triol, polyoxybutylene glycol, polytetramethylene ether glycol (PTMG), polymer polyol, poly (ethylene adipate), poly (diethylene adipate), poly (propylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate) ), Poly (neopentylene adipate), poly- ⁇ -caprolactone, poly (hexamethylene carbonate) Sulfonate) and the like.
- a natural polyol compound such as castor oil may be used.
- the equivalent ratio of the polyol and the polyisocyanate in producing the urethane prepolymer is, for example, an equivalent ratio of the isocyanate group in the polyisocyanate to the hydroxy group in the polyol (NCO group / OH group) of 1.2 or more and 2.2. Or less, more preferably 1.5 or more and 1.8 or less.
- the number average molecular weight of the urethane prepolymer is 2000 or more, preferably 2000 or more and 15000 or less, and more preferably 2000 or more and 10,000 or less.
- Carbon black is not particularly limited, and commercially available carbon black can be used. Examples of the carbon black include N110, N220, N330, N550, N770, and the like, or a mixture thereof according to the American Society for Testing Materials standard.
- the amount of the carbon black blended is 100 parts by mass of the urethane prepolymer in that the resulting composition of the present embodiment has sufficient mechanical strength and can impart viscosity and thixotropy (hangability) excellent in handleability. It is preferable that they are 10 mass parts or more and 120 mass parts or less with respect to 20 mass parts or more and 90 mass parts or less.
- drooping property means the shape maintenance property (it is also called thixotropy) after apply
- the preliminary composition may contain a filler, a plasticizer and the like in addition to the urethane prepolymer and carbon black.
- the filler compounded in the preliminary composition is not particularly limited.
- Fillers carbonates, organic bentonite, high styrene resin, coumarone-indene resin, phenol resin, formaldehyde resin, modified melamine resin, cyclized rubber, lignin, ebonite powder, shellac, cork powder, bone powder, wood powder, cellulose powder, Coconut palm tree on a tree
- Organic fillers such as pulp; lamp black, titanium white, bengara, titanium yellow, zinc white, red lead, cobalt blue, iron black, aluminum powder and other in
- calcium carbonate in order to impart desired characteristics.
- These calcium carbonates are not particularly limited, and commercially available products can be used.
- Examples of calcium carbonate include heavy calcium carbonate and precipitated calcium carbonate. Among these, heavy calcium carbonate is preferable from the viewpoint of imparting deep part curability to the composition of the present embodiment to be obtained.
- These fillers can be used singly or in combination of two or more.
- the amount of calcium carbonate blended is 10 masses with respect to 100 parts by mass of the urethane prepolymer in that the surface layer and the inside of the composition of the present embodiment have a good property of being cured almost uniformly (called deep part curability). Part to 100 parts by mass, more preferably 20 parts to 80 parts by mass.
- the plasticizer blended in the preliminary composition is not particularly limited.
- phthalic acid plasticizers and adipic acid plasticizers are preferred.
- phthalic acid plasticizer examples include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dilauryl phthalate (DLP), butyl benzyl phthalate (BBP), diisodecyl phthalate (DIDP), diisononyl phthalate (DINP), and dimethyl phthalate. And diethyl phthalate. Of these, diisononyl phthalate and diisodecyl phthalate are preferable.
- adipic acid plasticizer examples include dioctyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate, propylene glycol polyester adipate, and butylene glycol polyester adipate. Of these, diisononyl adipate is preferable.
- plasticizers include, for example, dibutyl sebacate, diisodecyl succinate, diethylene glycol dibenzoate, pentaerythritol ester, butyl oleate, methyl acetylricinoleate, trioctyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) ) Phosphate, tricresyl phosphate, tributyl trimellitate (TBTM), trioctyl trimellitate (TOTM), epoxy stearate alkyl, epoxidized soybean oil; acrylic oligomers such as butyl acrylate having a molecular weight of 500 to 10,000 Can be mentioned. These may be used alone or in combination of two or more.
- the compounding amount of the plasticizer is 10 parts by mass or more and 120 parts by mass with respect to 100 parts by mass of the urethane prepolymer from the viewpoint that the composition of the present embodiment has appropriate flexibility and has a viscosity excellent in handleability. It is preferably no greater than 30 parts by weight and more preferably no less than 30 parts by weight and no greater than 100 parts by weight.
- the blending amount of the plasticizer is within the above range, the sagability and workability of the composition of this embodiment are improved.
- the content of the plasticizer in the composition is the amount of the plasticizer used for the production of the urethane prepolymer and the plasticizer mixed later. It is the sum of the quantity.
- the production method of the preliminary composition is not particularly limited, and the amount of each component is not particularly limited as long as the amount does not deviate from the object of the present embodiment.
- the adhesion-imparting agent comprises a compound (A) obtained by reacting diisocyanate and trimethylolpropane (TMP) or glycerin so that the equivalent ratio of isocyanate group to hydroxyl group is 1.8 or more and 2.2 or less, and diisocyanate. Any one or both of the compound (B) which is a burette form or an isocyanurate form.
- Compound (A) and compound (B) are polyisocyanate compounds having three or more NCO groups.
- the diisocyanate compound is not particularly limited as long as it has two isocyanate groups (NCO groups) in the molecule.
- Specific examples of the diisocyanate compound include paraphenylene diisocyanate, tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′- Aromatic isocyanates such as 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
- an aliphatic isocyanate can be used.
- 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.
- Compound (A) is a diisocyanate addition obtained by reacting the above diisocyanate compound with trimethylolpropane (TMP) or glycerin so that the equivalent ratio of isocyanate group to hydroxy group is 1.8 or more and 2.2 or less. Is the body.
- TMP trimethylolpropane
- diisocyanate adduct examples include, for example, HDI-TMP or glycerin adduct obtained by reacting HDI with TMP or glycerin, and XDI-TMP or glycerine adduct obtained by reacting XDI with TMP or glycerin.
- TDI-TMP or glycerin adduct obtained by reacting TDI with TMP or glycerin
- TMXDI-TMP or glycerine adduct obtained by reacting TMXDI with TMP or glycerin
- HXDI- obtained by reacting HXDI with TMP examples thereof include TMP or glycerin adduct, IPDI-TMP or glycerin adduct obtained by reacting IPDI with TMP or glycerin, and the like.
- HDI-TMP adducts obtained by reacting HDI with TMP from the viewpoint of improving adhesiveness, HDI-TMP adducts obtained by reacting HDI with TMP, XDI-TMP adducts obtained by reacting XDI with TMP, etc. are preferably mentioned. Can do.
- the synthesis of the compound (A) can be carried out in the same manner as in the production of a normal urethane prepolymer.
- the above-mentioned equivalent ratio of the diisocyanate compound and trimethylolpropane (TMP) or glycerin is 50 ° C. or more and 100 It can be performed by heating and stirring at a temperature of °C or less.
- urethanation catalysts such as an organic tin compound, organic bismuth, and an amine, etc. can also be used as needed.
- HDI-TMP adduct a commercially available product can be used. Specific examples include D160N manufactured by Takeda Pharmaceutical Company Limited. Specific examples of the XDI-TMP adduct include D110N manufactured by Takeda Pharmaceutical Company Limited.
- the content of the compound (A) is 0.1 parts by mass or more and 5.0 parts by mass or less, preferably 0.3 parts by mass or more and 3.0 parts by mass or less, with respect to 100 parts by mass of the preliminary composition. More preferably, they are 0.5 mass part or more and 2.0 mass parts or less.
- the content of the compound (A) is less than 0.1 parts by mass, the composition of this embodiment is not preferable because the adhesiveness is deteriorated.
- the content of the compound (A) is more than 5.0 parts by mass, the composition of the present embodiment is apt to be brittle, and the elongation at break is deteriorated.
- the composition of the present embodiment has a fast adhesive development and good curability and sufficient adhesiveness, and has a good crosslinking density and the cured product is brittle. Excellent elongation at break because it does not become.
- Compound (B) is a diisocyanate burette or isocyanurate.
- diisocyanate burettes and isocyanurates include hexamethylene diisocyanate burette (hereinafter also referred to as “HDI burette”) and hexamethylene diisocyanate isocyanurate (hereinafter also referred to as “HDI isocyanurate”).
- the body is mentioned.
- the HDI buret body is represented by the following formula (I), for example.
- the HDI isocyanurate body is represented by the following formula (II), for example.
- the HDI burette represented by the above formula (I) and the HDI isocyanurate represented by the above formula (II) can be synthesized by a known method. Moreover, a commercial item can be used. Examples of commercially available HDI burettes include D-165N manufactured by Mitsui Chemicals Polyurethanes. Examples of commercially available HDI isocyanurates include D-170N, D-170HN, D-172N, and D-177N manufactured by Mitsui Chemical Polyurethanes.
- HDI burettes and HDI isocyanurates can be suitably used for automobiles because of their high adhesion-imparting effect.
- the content of the compound (B) is 0.1 parts by mass or more and 5 parts by mass or less, preferably 0.3 parts by mass or more and 3.0 parts by mass or less, with respect to 100 parts by mass of the preliminary composition. Preferably they are 0.5 to 2.0 mass parts.
- the content of the compound (B) is less than 0.1 parts by mass, the composition of this embodiment is not preferable because the adhesiveness is deteriorated.
- the content of the compound (B) is more than 5 parts by mass, the composition of the present embodiment is apt to be brittle, and the elongation at break is deteriorated.
- the content of the compound (B) is within the above range, the composition of the present embodiment has high adhesiveness, good curability, sufficient adhesiveness, and excellent elongation at break.
- the content in the case where both the compound (A) and the compound (B) are included in the adhesion-imparting agent is such that the content of the compound (A) is A part by mass, and the content of the compound (B) is B part by mass. Then, the following formula (1) is satisfied with respect to 100 parts by mass of the preliminary composition. 0.1 ⁇ (A + B) ⁇ 5 (1)
- the content of the adhesion-imparting agent is 0.1 part by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the preliminary composition as the total amount of the compound (A) and the compound (B), preferably Is 0.3 to 3.0 parts by mass, more preferably 0.5 to 2.0 parts by mass.
- the content of the adhesion-imparting agent is less than 0.1 parts by mass, the composition of the present embodiment is not preferable because the adhesiveness deteriorates.
- the content of the adhesion-imparting agent is more than 5.0 parts by mass, the composition of the present embodiment is not preferable because the composition tends to be brittle and the elongation at break deteriorates.
- the composition of the present embodiment has excellent adhesion without performing a ground treatment on a difficult-to-adhere adherend, and characteristics such as elongation at break. Can also be satisfied.
- the first catalyst is obtained by reacting 1,3-diacetoxy-1,1,3,3-tetrabutyldistanoxane and ethyl silicate within a molar ratio of 1: 0.8 or more and 1: 1.2 or less.
- One or both of the compound (C) obtained in this way and dibutyltin bis (pentadione) are contained.
- Compound (C) is a reaction product of a tin catalyst and a silicate compound.
- the composition of the present embodiment can adhere the adherend to the adherend that is difficult to adhere to without performing a ground treatment, Excellent adhesion to various adherends such as adhesive coating plates.
- Compound (C) has a molar ratio of 1,3-diacetoxy-1,1,3,3-tetrabutyldistanoxane and ethyl silicate represented by the following formula (III) in a molar ratio of 1: 0.8 or more and 1: It is obtained by reacting within the range of 1.2 or less.
- 1,3-diacetoxy-1,1,3,3-tetrabutyldistanoxane represented by the above formula (III) is an organotin catalyst and can be synthesized by a known method. For example, it can be obtained by reacting a dialkyltin carboxylate obtained by reacting a dialkyltin oxide with an organic acid composed of a monocarboxylic acid or a monocarboxylic anhydride and an alkoxysilane.
- Compound (C) can be synthesized by a known method. For example, 1,3-diacetoxy-1,1,3,3-tetrabutyldistanoxane and ethyl silicate are mixed so that the molar ratio is in the range of 1: 0.8 or more and 1: 1.2 or less. Can be obtained by reacting at a temperature of 100 ° C. to 130 ° C. for 1 hour to 3 hours.
- the content of the compound (C) is 0.001 parts by mass or more and 0.5 parts by mass or less, preferably 0.005 parts by mass or more and 0.3 parts by mass or less, with respect to 100 parts by mass of the preliminary composition. More preferably, they are 0.01 mass part or more and 0.1 mass part or less.
- the content of the compound (C) is less than 0.001 part by mass, the composition of this embodiment is not preferable because the adhesiveness is deteriorated.
- the content of the compound (C) is more than 0.5 parts by mass, the composition of the present embodiment is not preferable because the heat resistant adhesiveness is deteriorated.
- the content of the compound (C) is within the above range, the composition of the present embodiment has good adhesiveness and heat resistant adhesiveness.
- Dibutyltin bis (pentadione) is a hexavalent organic tin compound and a tin-based metal catalyst, and is represented by the following formula (IV).
- the composition of the present embodiment can adhere the adherend to the adherend that is difficult to adhere without performing a ground treatment, Excellent adhesion to various adherends such as hard-to-adhere coated plates.
- dibutyltin bis (pentadione) a commercially available product can be used. Specific examples include Neostan U-220H manufactured by Nitto Chemical Co., Ltd.
- the content of dibutyltin bis (pentadione) is 0.001 part by mass or more and 0.5 part by mass or less, preferably 0.005 part by mass or more and 0.3 part by mass or less with respect to 100 parts by mass of the preliminary composition. More preferably, it is 0.01 mass part or more and 0.1 mass part or less.
- the composition of this embodiment is not preferable because the adhesiveness deteriorates.
- the content of dibutyltin bis (pentadione) is more than 0.5 parts by mass, the composition of this embodiment is not preferable because the heat resistant adhesiveness is deteriorated.
- the content of dibutyltin bis (pentadione) is within the above range, the composition of this embodiment has good adhesion and heat-resistant adhesion.
- the first catalyst contains both the compound (C) and dibutyltin bis (pentadione)
- the content of the compound (C) is C parts by mass
- the content of dibutyltin bis (pentadione) is D.
- the relationship of the following formula (2) is satisfied. 0.001 ⁇ (C + D) ⁇ 0.5 (2)
- the content of the first catalyst is 0.001 part by mass or more and 0.5 part by mass or less with respect to 100 parts by mass of the preliminary composition as the total amount of the compound (C) and dibutyltin bis (pentadione). Yes, preferably 0.005 parts by mass or more and 0.3 parts by mass or less, more preferably 0.01 parts by mass or more and 0.1 parts by mass or less.
- the content of the first catalyst is less than 0.001 part by mass, the composition of the present embodiment is not preferable because the adhesiveness is deteriorated.
- the content of the first catalyst is more than 0.5 parts by mass, the composition of the present embodiment is not preferable because the heat resistant adhesiveness is deteriorated.
- the composition of the present embodiment has excellent adhesiveness without subjecting the adherend, which is difficult to adhere, to heat resistance, and fracture. Properties such as elongation can also be satisfied.
- composition of the present embodiment contains the first catalyst, it catalyzes the reaction between the isocyanate group of the urethane prepolymer and the active hydrogen on the adherend surface. Excellent adhesion to various adherends and excellent heat-resistant adhesion. Further, the first catalyst can maintain the viscosity of the urethane prepolymer well.
- the second catalyst contains dimorpholinodiethyl ether (DMDEE) represented by the following formula (V) which is an amine catalyst. Since dimorpholinodiethyl ether catalyzes the reaction between the isocyanate group of the urethane prepolymer and moisture in the air, the resulting composition is excellent in curability and sag. In addition, since dimorpholinodiethyl ether (DMDEE) hardly catalyzes the reaction between an isocyanate group and active hydrogen other than water, the resulting composition is excellent in storage stability.
- DMDEE dimorpholinodiethyl ether
- n 0 or 1
- DMDEE dimorpholinodiethyl ether
- the content of dimorpholinodiethyl ether is 0.01 parts by mass or more and 2.0 parts by mass or less, preferably 0.05 parts by mass or more and 1. part by mass with respect to 100 parts by mass of the preliminary composition. 5 parts by mass or less, more preferably 0.05 parts by mass or more and 1.0 parts by mass or less. If the content of dimorpholinodiethyl ether is less than 0.01 parts by mass or more than 2.0 parts by mass, the composition of this embodiment is not preferable because the curability and high-temperature and high-humidity adhesiveness deteriorate.
- the composition of the present embodiment has excellent adhesion without performing a ground treatment on an adherend that is difficult to adhere, and is curable and has a high temperature. Excellent wet adhesion, drooping and storage stability.
- the second catalyst can further contain N, N-dimethylaminoethylmorpholine represented by the following formula (VI), which is an amine catalyst. Since N, N-dimethylaminoethylmorpholine catalyzes the reaction between the isocyanate group of the urethane prepolymer and moisture in the air, the resulting composition is excellent in high-temperature and high-humidity adhesiveness and curability.
- VI N, N-dimethylaminoethylmorpholine represented by the following formula (VI), which is an amine catalyst. Since N, N-dimethylaminoethylmorpholine catalyzes the reaction between the isocyanate group of the urethane prepolymer and moisture in the air, the resulting composition is excellent in high-temperature and high-humidity adhesiveness and curability.
- the content of N, N-dimethylaminoethylmorpholine is based on 100 parts by mass of the preliminary composition when the content of N, N-dimethylaminoethylmorpholine is F parts by mass.
- the following formula (4) is satisfied. F ⁇ 2 (4)
- the content of N, N-dimethylaminoethylmorpholine is 2.0 parts by mass or less, preferably 0.1 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the preliminary composition. Yes, and more preferably 0.5 parts by mass or more and 1.0 parts by mass or less. If the content of N, N-dimethylaminoethylmorpholine is less than 0.1 parts by mass, the composition of this embodiment is unfavorable because the curability deteriorates. When the content of N, N-dimethylaminoethylmorpholine is more than 2.0 parts by mass, the composition of the present embodiment is not preferable because the curability, the drooping property and the storage stability are deteriorated.
- the composition of the present embodiment has excellent adhesiveness without subjecting the hardly adherend to the adherend, Excellent high-temperature and high-humidity adhesiveness and curability.
- the second catalyst contains both dimorpholinodiethyl ether and N, N-dimethylaminoethylmorpholine
- the content of dimorpholinodiethyl ether is E parts by mass
- the content of aminoethylmorpholine is F parts by mass
- the following formulas (5) and (6) are satisfied with respect to 100 parts by mass of the preliminary composition.
- the content of the second catalyst is 0.1 parts by mass or more and 2.0 parts by mass with respect to 100 parts by mass of the preliminary composition as a total amount of dimorpholinodiethyl ether and N, N-dimethylaminoethylmorpholine. Part or less, preferably 0.3 parts by weight or more and 1.5 parts by weight or less, more preferably 0.5 parts by weight or more and 1.0 parts by weight or less. Further, the content of dimorpholinodiethyl ether in the second catalyst is preferably larger than the content of N, N-dimethylaminoethylmorpholine.
- the composition of the present embodiment is not preferable because the curability and high-temperature and high-humidity adhesiveness deteriorate.
- the content of the second catalyst is more than 2.0 parts by mass, the composition of the present embodiment is not preferable because curability, high-temperature and high-humidity adhesion, drooping property, and storage stability are deteriorated.
- the composition of the present embodiment has excellent adhesiveness without subjecting the adherend, which is difficult to adhere, to curability and high temperature and high humidity adhesion. Excellent in stability, sag and storage stability.
- the composition of this embodiment contains additives as long as it does not impair the purpose of the present invention.
- additives include plasticizers, fillers, adhesion promoters, and curing accelerators (catalysts), as well as curing agents, reactive diluents, thixotropic agents, silane coupling agents, pigments, dyes, and aging.
- curing agents include an inhibitor, an antioxidant, an antistatic agent, a flame retardant, a drying oil, an adhesiveness imparting agent, a dispersant, a dehydrating agent, an ultraviolet absorber, and a solvent.
- Additives and the like can be kneaded by a general method to form a composition and used for 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.
- the method for producing the composition of the present embodiment is not particularly limited.
- an adhesion-imparting agent, a first catalyst, a second catalyst, and an optional component are added to the preliminary composition, and are sufficiently kneaded under reduced pressure to form a one-component moisture-curable composition that is the composition of the present embodiment. Can do.
- the method for using the composition of the present embodiment is not particularly limited. For example, after applying to an adherend, it is bonded to a non-adherent body, and both adherends are pressure-bonded to form an adhesive structure.
- the composition of the present embodiment includes a preliminary composition, an adhesion-imparting agent containing any one or both of the compound (A) and the compound (B), the compound (C), and dibutyltin bis (pentadione). ) And a second catalyst containing dimorpholino diethyl ether, respectively, within a predetermined range. Therefore, the composition of the present embodiment has excellent adhesion for adhering a glass adherend without performing a ground treatment on an adherend that is difficult to adhere, and high-temperature and high-humidity adhesion, curing speed, drooping property Further, properties such as storage stability, heat resistant adhesiveness and elongation at break can also be satisfied.
- composition of this embodiment can be used as an adhesive for adhering to the painted surface and glass of an automobile, and can adhere a window glass to a vehicle without using a primer.
- compositions, the application conditions, and the like of the present embodiment are not particularly limited.
- the composition of the automobile such as an adhesive used for bonding the vehicle body and the window glass is used.
- it is suitably used as an adhesive for so-called hard-to-adhere coating plates coated with high solid paint, acid rain-resistant paint, easy maintenance paint, and the like.
- composition of the present embodiment will be specifically described by way of examples. However, this embodiment is not limited to these.
- urethane prepolymer 200 g of polypropylene ether triol having a number average molecular weight of 5000 (G-5000, trade name “EXCENOL5030”, manufactured by Asahi Glass Co., Ltd.) and 600 g of polypropylene ether diol having a number average molecular weight of 2000 (D-2000, trade name “EXCENOL2020”, Asahi Glass Co., Ltd.) was heated to 100 ° C. to 130 ° C., stirred while degassing, and dehydrated until the water content became 0.01% or less.
- ⁇ Preparation of preliminary composition 100 parts by mass of the urethane prepolymer thus obtained, 70 parts by mass of carbon black (trade name: Elftec 8, manufactured by Cabot), calcium carbonate (heavy calcium carbonate, trade name: SB blue, Shiraishi Calcium) 20 parts by mass) and 50 parts by mass of a plasticizer (diisononyl phthalate (DINP), manufactured by Mitsubishi Chemical) were added and mixed for 1 hour using a mixer under vacuum to obtain a preliminary composition.
- carbon black trade name: Elftec 8, manufactured by Cabot
- calcium carbonate heavy calcium carbonate, trade name: SB blue, Shiraishi Calcium
- a plasticizer diisononyl phthalate (DINP), manufactured by Mitsubishi Chemical
- the compound (C) was obtained by reacting under stirring at a temperature of 65 ° C. or lower for 24 hours.
- composition obtained above was evaluated for high-temperature and high-humidity adhesiveness, curing speed, drooping property, storage stability, heat-resistant adhesiveness, elongation at break, and adhesiveness (coated plates 1 to 3) by the following methods. The results are shown in Tables 1-5.
- a glass primer (trade name: MS-90, manufactured by Yokohama Rubber Co., Ltd.) was applied to a glass adherend for evaluation of adhesion, allowed to stand at 20 ° C. for 2 minutes, and then each composition obtained above was 3 mm thick.
- the test specimen was coated in a bead shape. The specimen was left for 3 hours in an atmosphere of 20 ° C. and 60 RH%, and then immersed in warm water at 40 ° C. for 24 hours. Thereafter, one end of the cured product of each composition formed on the test body was gripped and peeled 180 degrees to evaluate the fracture state. Tables 1 to 5 show the evaluation results of the destruction state.
- CF is the area ratio of cohesive fracture of the cured product
- AF is the area ratio of interfacial fracture between the coated plate / cured product
- PS is the area ratio of interfacial fracture between the primer composition / cured product.
- FIG. 1 is a conceptual diagram illustrating an example of a drooping test.
- each composition 1 obtained above is extruded into a band shape with a right triangle bead having a base of 6 mm and a height of 10 mm on a glass plate 3 having a thickness of 5 mm, and a holder 4 is immediately attached to the glass plate 3.
- the distance h at which the top of each composition 2 hangs down after being left for 30 minutes in an atmosphere of 20 ° C. and 65 RH% was measured at an angle of 90 °.
- the distance h was evaluated as good when 0 mm, the distance h exceeded 0 mm and 1.5 mm or less was evaluated as good, and the others were evaluated as inferior.
- Tables 1-5 The results are shown in Tables 1-5.
- a glass primer (trade name: MS-90, manufactured by Yokohama Rubber Co., Ltd.) was applied to a glass adherend for evaluation of adhesion, allowed to stand at 20 ° C. for 2 minutes, and then each composition obtained above was 3 mm thick.
- the test specimen was coated in a bead shape. This specimen was left for 7 days in an atmosphere of 20 ° C. and 60 RH%, then left for 5 days in an atmosphere of 120 ° C., and gradually cooled to 20 ° C. Thereafter, one end of the cured product of each composition formed on the test body was gripped and peeled 180 degrees to evaluate the fracture state. Tables 1 to 5 show the evaluation results of the destruction state.
- CF is the area ratio of cohesive fracture of the cured product
- AF is the area ratio of interfacial fracture between the coated plate / cured product
- PS is the area ratio of interfacial fracture between the primer composition / cured product.
- CF is the area ratio of cohesive fracture of the cured product
- AF is the area ratio of interfacial fracture between the coated plate / cured product
- PS is the area ratio of interfacial fracture between the primer composition / cured product.
- -Preliminary composition Composition obtained by the above preparation-Compound (A): Adhesion imparting agent, compound obtained by synthesis-Compound (B): Adhesion imparting agent, HDI burette body, trade name “Takenate D-165N”, manufactured by Mitsui Chemicals, Inc. • Compound (C): first catalyst, compound obtained by the above synthesis • Dibutyltin bis (pentadione): first catalyst, trade name “Neostan U-810” ⁇ Nitto Kasei Kogyo Co., Ltd. ⁇ Dimorpholinodiethyl ether: second catalyst, trade name “DMDEE”, San Apro Co., Ltd.
- N, N-dimethylaminoethylmorpholine second catalyst, trade name “X-DM”, air Products ⁇ TDI isocyanurate: Trade name “Desmodur IL 1351”, Bayer ⁇ Dibutyltin dilaurate: Trade name “Neostan U-100”, Nitto Kasei Kogyo Made by
- the cured products of the compositions of Comparative Examples 1 to 15 and 22 to 24 are inferior in adhesiveness because either the heat-resistant adhesiveness or the adhesiveness (coated plate 1 to 3) becomes interfacial peeling (AF or PS).
- AF or PS interfacial peeling
- the cured product of each composition of Comparative Examples 1 to 32 has any one of high temperature and high humidity adhesiveness, curing speed, drooping property, storage stability, heat resistant adhesiveness, elongation at break and adhesiveness (coated plates 1 to 3). Inferiority was confirmed.
- each of the preliminary composition containing a urethane prepolymer having an isocyanate group at the terminal and carbon black, a predetermined adhesion-imparting agent, a predetermined first catalyst, and a predetermined second catalyst is specified.
- the related composition has excellent adhesion to adhere the glass adherend to the hard-to-adhere adherend without performing the surface treatment, and high temperature and high humidity adhesion, curing speed, drooping property, storage stability. It has been found that properties such as heat resistance, heat-resistant adhesiveness and elongation at break can also be satisfied.
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Abstract
Description
(1) 末端にイソシアネート基を有するウレタンプレポリマーとカーボンブラックとを含む予備組成物と、
ジイソシアネートとトリメチロールプロパンまたはグリセリンとをイソシアネート基と水酸基との当量比が1.8以上2.2以下となるように反応させて得られる化合物(A)と、ジイソシアネートのビュレット体またはイソシアヌレート体である化合物(B)との何れか一方または両方を含む接着付与剤と、
1,3-ジアセトキシ-1,1,3,3-テトラブチルジスタノキサンとエチルシリケートとをモル比が1:0.8~1:1.2の範囲内で反応させて得られる化合物(C)と、ジブチル錫ビス(ペンタジオン)との何れか一方または両方を含む第1触媒と、
ジモルフォリノジエチルエーテルを含む第2触媒と、
を含み、
前記化合物(A)の含有量をA質量部、前記化合物(B)の含有量をB質量部、前記化合物(C)の含有量をC質量部、前記ジブチル錫ビス(ペンタジオン)の含有量をD質量部、前記ジモルフォリノジエチルエーテルの含有量をE質量部としたとき、前記予備組成物100質量部に対して下記式(1)~(3)を満たすことを特徴とする一液湿気硬化型組成物。
0.1≦(A+B)≦5 ・・・(1)
0.001≦(C+D)≦0.5 ・・・(2)
0.01≦E≦2 ・・・(3)
(2) 前記第2触媒は、さらにN,N-ジメチルアミノエチルモルフォリンを含み、
前記N,N-ジメチルアミノエチルモルフォリンの含有量をF質量部としたとき、前記予備組成物100質量部に対して下記式(4)を満たす上記(1)に記載の一液湿気硬化型組成物。
F≦2 ・・・(4)
(3) 前記予備組成物100質量部に対して下記式(5)、(6)を満たす上記(1)または(2)に記載の一液湿気硬化型組成物。
F≦E ・・・(5)
0.1≦(E+F)≦2 ・・・(6)
(4) 前記ジイソシアネートが、ヘキサメチレンジイソシアネートである上記(1)から(3)の何れか1つに記載の一液湿気硬化型組成物。
予備組成物は、末端にイソシアネート基を有するウレタンプレポリマーとカーボンブラックとを含んでいる。
ウレタンプレポリマーは、分子内に複数のイソシアネート基を分子末端に含有するプレポリマーである。ウレタンプレポリマーは、取り扱いの観点から室温で液状であるものが好ましい。ウレタンプレポリマーの作製方法は、特に制限されるものではなく、従来より公知の方法が挙げられる。ウレタンプレポリマーは、例えば、ポリイソシアネート化合物とポリオール化合物とを、イソシアネート基(NCO基)がヒドロキシ基(OH基)に対して過剰となるように反応させることにより得られる反応生成物である。ウレタンプレポリマーは、一般に、0.5質量%以上10質量%以下のNCO基を分子末端に含有するものである。このイソシアネート基は、芳香族炭化水素、脂肪族炭化水素のいずれに結合していてもよい。
カーボンブラックは、特に限定されず、通常市販されているものを用いることができる。カーボンブラックとしては、例えば、米国材料試験協会規格における、N110、N220、N330、N550、N770等あるいはこれらの混合物が挙げられる。
接着付与剤は、ジイソシアネートとトリメチロールプロパン(TMP)またはグリセリンとをイソシアネート基と水酸基との当量比が1.8以上2.2以下となるように反応させて得られる化合物(A)と、ジイソシアネートのビュレット体またはイソシアヌレート体である化合物(B)との何れか一方または両方を含む。化合物(A)および化合物(B)は、3個以上のNCO基を有するポリイソシアネート化合物である。
(ジイソシアネート化合物)
ジイソシアネート化合物は、分子内にイソシアネート基(NCO基)を2個有するものであれば特に限定されない。ジイソシアネート化合物としては、具体的には、例えば、パラフェニレンジイソシアネート、トリレンジイソシアネート(TDI)、ナフタレンジイソシアネート(NDI)、4,4’ージフェニルメタンジイソシアネート(4,4’-MDI)、2,4’-ジフェニルメタンジイソシアネート(2,4’-MDI)、トリジンジイソシアネート(TODI)等の芳香族イソシアネート;テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート(HDI)、トリメチルヘキサメチレンジイソシアネート(TMHDI)、リジンジイソシアネート、ノルボルナンジイソシアネート(NBDI)、オクタデシルジイソシアネート等の脂肪族イソシアネート;トランスシクロヘキサン-1,4-ジイソシアネート、イソホロンジイソシアネート(IPDI)、ジシクロヘキシルメタンジイソシアネート(H12MDI)等の脂環式イソシアネート;キシレンジイソシアネート(XDI)、水素添加キシリレンジイソシアネート(HXDI)、テトラメチルキシリレンジイソシアネート(TMXDI)等のアリール脂肪族イソシアネート;上記各イソシアネートの変性イソシアネート等が挙げられる。これらは、それぞれ1種単独でまたは2種以上を組み合わせて使用することができる。
化合物(B)は、ジイソシアネートのビュレット体またはイソシアヌレート体である。ジイソシアネート化合物のビュレット体、イソシアヌレート体としては、例えば、ヘキサメチレンジイソシアネートのビュレット(以下、「HDIビュレット」ともいう。)体、ヘキサメチレンジイソシアネートのイソシアヌレート(以下、「HDIイソシアヌレート」ともいう。)体が挙げられる。HDIビュレット体は、例えば、下記式(I)で表される。HDIイソシアヌレート体は、例えば、下記式(II)で表される。
0.1≦(A+B)≦5 ・・・(1)
第1触媒は、1,3-ジアセトキシ-1,1,3,3-テトラブチルジスタノキサンとエチルシリケートとをモル比が1:0.8以上1:1.2以下の範囲内で反応させて得られる化合物(C)と、ジブチル錫ビス(ペンタジオン)との何れか一方または両方を含んでいる。
化合物(C)は、錫系触媒と珪酸エステル化合物との反応物である。第1触媒として、化合物(C)を含有することにより、本実施形態の組成物は、難接着な被着体に対して下地処理を行うことなく被着体を接着させることができ、難接着性塗板等の種々の被着体との接着性に優れる。
ジブチル錫ビス(ペンタジオン)は、6価の有機錫化合物であり錫系の金属触媒であり、下記式(IV)で表される。第1触媒として、ジブチル錫ビス(ペンタジオン)を含有することにより、本実施形態の組成物は、難接着な被着体に対して下地処理を行うことなく被着体を接着させることができ、難接着性塗板等の種々の被着体との接着性に優れる。
0.001≦(C+D)≦0.5 ・・・(2)
第2触媒は、アミン系触媒である下記式(V)で表されるジモルフォリノジエチルエーテル(DMDEE)を含有する。ジモルフォリノジエチルエーテルは、ウレタンプレポリマーのイソシアネート基と空気中の水分との反応を触媒するので、得られる組成物は硬化性、垂下性に優れる。また、ジモルフォリノジエチルエーテル(DMDEE)は、イソシアネート基と水以外の活性水素との反応を触媒しにくいので、得られる組成物は貯蔵安定性に優れる。
0.01≦E≦2 ・・・(3)
F≦2 ・・・(4)
F≦E ・・・(5)
0.1≦(E+F)≦2 ・・・(6)
数平均分子量5000のポリプロピレンエーテルトリオール200g(G-5000、商品名「EXCENOL5030」、旭硝子株式会社製)と、数平均分子量2000のポリプロピレンエーテルジオール600g(D-2000、商品名「EXCENOL2020」、旭硝子株式会社製)とをフラスコに投入して、100℃~130℃に加熱し、脱気しながら攪拌して水分率が0.01%以下になるまで脱水した。その後、90℃まで冷却し、ジフェニルメタンジイソシアネート(MDI、商品名「スミジュール44S」、住化バイエルウレタン株式会社製)を、NCO基/OH基のモル比が1.8となる量を添加した後、約24時間、窒素雰囲気下で反応を進めNCO含有量が2.0%のウレタンプレポリマーを作製した。
このようにして得られたウレタンプレポリマー100質量部に、カーボンブラック(商品名:エルフテック8、キャボット社製)70質量部、炭酸カルシウム(重質炭酸カルシウム、商品名:SB青、白石カルシウム社製)20質量部、可塑剤(フタル酸ジイソノニル(DINP)、三菱化学社製)50質量部を添加し真空下でミキサーを用いて1時間混合し、予備組成物を得た。
HDI(商品名:デュラネート50M-HDI、NCO基:50質量%、旭化成ケミカルズ社製)100gを撹拌しながら、N2気流中でNCO基/OH基が2.0となるように、1,1,1-トリメチロールプロパン(三菱ガス化学社製)245gをメチルエチルケトン(MEK)に溶解させたものをHDIに滴下しながら反応させることで化合物(A)(NCO基:22.2質量%)を得た。
1,3-ジアセトキシ-1,1,3,3-テトラブチルジスタノキサン(大阪新薬社製)100gとエチルシリケート(テトラエトキシシラン、エルコート社製288gとを均一に混合して反応温度55℃以上65℃以下の条件下で24時間攪拌して反応させて、化合物(C)を得た。
表1~5に示す各成分を同表に示す添加量(質量部)で配合し、これらを均一に混合して、表1~5に示される実施例1~20、比較例1~32の各一液湿気硬化型組成物(以下、単に組成物という。)を調整した。各々の実施例、比較例における各成分の添加量(質量部)を表1~5に示す。
接着性評価用のガラス被着体にガラス用プライマー(商品名:MS-90、横浜ゴム社製)を塗布し、20℃で2分間放置した後、上記で得られた各組成物を3mm厚でビード状に塗布して試験体とした。この試験体を、20℃、60RH%の雰囲気下で3時間放置した後、40℃の温水に24時間浸漬させた。その後、この試験体に形成された各組成物の硬化物の一端を把持して180度剥離し、破壊状態を評価した。破壊状態の評価結果を表1~5に示す。CFは硬化物の凝集破壊の面積率であり、AFは塗板/硬化物間の界面破壊の面積率であり、PSはプライマー組成物/硬化物間の界面破壊の面積率である。CFであれば良好と評価した。結果を表1~5に示す。
接着性評価用のガラス被着体に上記で得られた各組成物を3mm厚でビード状に塗布して試験体とした。この試験体を、20℃、60RH%の雰囲気下に放置して、各組成物の表面に対してポリエチレンフィルムを密着させた後に引き上げてポリエチレンフィルムに対して各組成物が付着しなくなるまでの時間(皮張り時間)を測定した。皮張り時間が20分以上70分以下を○と評価し、70分を超え100分未満を△と評価し、それ以外は×と評価した。○、△であれば良好と判断した。結果を表1~5に示す。
垂下性試験は、各組成物の形状維持性(チクソ性)を評価するものである。図1は、垂下性試験の一例を示す概念図である。図1に示すように、厚さ5mmのガラス板3に上記で得られた各組成物1を底辺6mm、高さ10mmの直角三角形ビードで帯状に押し出し、直ちにガラス板3に保持具4を取り付け90°の角度に保持し、20℃、65RH%の雰囲気下で30分放置後の各組成物2の頂点の垂れ下がりの距離hを測定した。距離hが0mmを良好と評価し、距離hが0mmを超え1.5mm以下を良と評価し、それ以外は劣ると評価した。結果を表1~5に示す。
上記で得られた各組成物を密閉容器に充填して窒素置換し、40℃の雰囲気下で7日間放置し、その後、押出し粘度を測定して初期粘度に対する増粘率(%)を求めた。増粘率が20%以下を良好と評価し、20%を超え25%未満を良と評価し、25%以上を劣ると評価した。結果を表1~5に示す。
接着性評価用のガラス被着体にガラス用プライマー(商品名:MS-90、横浜ゴム社製)を塗布し、20℃で2分間放置した後、上記で得られた各組成物を3mm厚でビード状に塗布して試験体とした。この試験体を、20℃、60RH%の雰囲気下で7日間放置した後、120℃の雰囲気下で5日間放置し、20℃まで徐冷した。その後、この試験体に形成された各組成物の硬化物の一端を把持して180度剥離し、破壊状態を評価した。破壊状態の評価結果を表1~5に示す。CFは硬化物の凝集破壊の面積率であり、AFは塗板/硬化物間の界面破壊の面積率であり、PSはプライマー組成物/硬化物間の界面破壊の面積率である。CFであれば良好と評価した。結果を表1~5に示す。
上記で得られた各組成物の硬化物を厚さ2mmのダンベル状試験片(ダンベル状3号形)に切り出し、JIS K6251-1993に準拠して、破断伸び(%)を測定した。破断伸びが300%以上を良好と評価し、270%以上300%未満を良と評価し、それ以外は劣ると評価した。結果を表1~5に示す。
塗板1(酸エポキシ系塗板)、塗板2(酸エポキシ系塗板)、塗板3(アクリルメラミン系塗板)の表面をホワイトガソリンで洗浄した後に、それぞれプライマーを用いず直接に上記で得られた各組成物を3mm厚でビード状に塗布して試験体とした。この試験体を、20℃、60RH%の雰囲気下で7日間放置した後、40℃の温水に7日間浸漬させた。その後、20℃の雰囲気下で、この試験体に形成された各組成物の硬化物の一端を把持して180度剥離し、破壊状態を評価した。破壊状態の評価結果を表1~5に示す。CFは硬化物の凝集破壊の面積率であり、AFは塗板/硬化物間の界面破壊の面積率であり、PSはプライマー組成物/硬化物間の界面破壊の面積率である。CFであれば良好と評価した。結果を表1~5に示す。
・予備組成物:上記で調製して得られた組成物
・化合物(A):接着付与剤、上記で合成して得られた化合物
・化合物(B):接着付与剤、HDIビュレット体、商品名「タケネートD-165N」、三井化学社製
・化合物(C):第1触媒、上記で合成して得られた化合物
・ジブチル錫ビス(ペンタジオン):第1触媒、商品名「ネオスタンU-810」、日東化成工業社製
・ジモルフォリノジエチルエーテル:第2触媒、商品名「DMDEE」、サンアプロ社製
・N,N-ジメチルアミノエチルモルフォリン:第2触媒、商品名「X-DM」、エアープロダクツ社製
・TDIイソシアヌレート体:商品名「デスモジュールIL 1351」、バイエル社製
・ジブチル錫ジラウレート:商品名「ネオスタンU-100」、日東化成工業社製
Claims (4)
- 末端にイソシアネート基を有するウレタンプレポリマーとカーボンブラックとを含む予備組成物と、
ジイソシアネートとトリメチロールプロパンまたはグリセリンとをイソシアネート基と水酸基との当量比が1.8以上2.2以下となるように反応させて得られる化合物(A)と、ジイソシアネートのビュレット体またはイソシアヌレート体である化合物(B)との何れか一方または両方を含む接着付与剤と、
1,3-ジアセトキシ-1,1,3,3-テトラブチルジスタノキサンとエチルシリケートとをモル比が1:0.8~1:1.2の範囲内で反応させて得られる化合物(C)と、ジブチル錫ビス(ペンタジオン)との何れか一方または両方を含む第1触媒と、
ジモルフォリノジエチルエーテルを含む第2触媒と、
を含み、
前記化合物(A)の含有量をA質量部、前記化合物(B)の含有量をB質量部、前記化合物(C)の含有量をC質量部、前記ジブチル錫ビス(ペンタジオン)の含有量をD質量部、前記ジモルフォリノジエチルエーテルの含有量をE質量部としたとき、前記予備組成物100質量部に対して下記式(1)~(3)を満たすことを特徴とする一液湿気硬化型組成物。
0.1≦(A+B)≦5 ・・・(1)
0.001≦(C+D)≦0.5 ・・・(2)
0.01≦E≦2 ・・・(3) - 前記第2触媒は、さらにN,N-ジメチルアミノエチルモルフォリンを含み、
前記N,N-ジメチルアミノエチルモルフォリンの含有量をF質量部としたとき、前記予備組成物100質量部に対して下記式(4)を満たす請求項1に記載の一液湿気硬化型組成物。
F≦2 ・・・(4) - 前記予備組成物100質量部に対して下記式(5)、(6)を満たす請求項1または2に記載の一液湿気硬化型組成物。
F≦E ・・・(5)
0.1≦(E+F)≦2 ・・・(6) - 前記ジイソシアネートが、ヘキサメチレンジイソシアネートである請求項1から3の何れか1つに記載の一液湿気硬化型組成物。
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CN107406746A (zh) * | 2015-03-31 | 2017-11-28 | 横滨橡胶株式会社 | 粘接剂组合物 |
CN106167640A (zh) * | 2015-10-30 | 2016-11-30 | 丹阳市日月漆业有限公司 | 一种界面附着力增进剂及其制备方法和应用 |
JP2020122077A (ja) * | 2019-01-30 | 2020-08-13 | 横浜ゴム株式会社 | 一液湿気硬化型ポリウレタン組成物 |
JP7199238B2 (ja) | 2019-01-30 | 2023-01-05 | シーカ・ハマタイト株式会社 | 一液湿気硬化型ポリウレタン組成物 |
JP7466272B2 (ja) | 2019-01-30 | 2024-04-12 | シーカ テクノロジー アクチェンゲゼルシャフト | 一液湿気硬化型ポリウレタン組成物 |
JP2022549755A (ja) * | 2019-08-06 | 2022-11-29 | ダウ グローバル テクノロジーズ エルエルシー | 一成分型ポリウレタンプレポリマー組成物 |
JP7550213B2 (ja) | 2019-08-06 | 2024-09-12 | ダウ グローバル テクノロジーズ エルエルシー | 一成分型ポリウレタンプレポリマー組成物 |
JP7529622B2 (ja) | 2021-07-02 | 2024-08-06 | シーカ テクノロジー アクチェンゲゼルシャフト | ウレタン系接着剤組成物 |
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CN105026450B (zh) | 2018-03-09 |
JP7073297B2 (ja) | 2022-05-23 |
JP2019112651A (ja) | 2019-07-11 |
JPWO2014136800A1 (ja) | 2017-02-16 |
KR101778107B1 (ko) | 2017-09-13 |
US9834711B2 (en) | 2017-12-05 |
KR20150110754A (ko) | 2015-10-02 |
US20160002511A1 (en) | 2016-01-07 |
CN105026450A (zh) | 2015-11-04 |
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