WO2008029887A1

WO2008029887A1 - Polyol composition for polyolefin adhesive and use thereof

Info

Publication number: WO2008029887A1
Application number: PCT/JP2007/067429
Authority: WO
Inventors: Matsunori Yasuyoshi; Junichi Matsumoto; Takio Homma
Original assignee: Idemitsu Sartomer Kk
Priority date: 2006-09-07
Filing date: 2007-09-06
Publication date: 2008-03-13
Also published as: JP2008063425A; JP5097373B2

Abstract

Disclosed is a novel polyol composition which enables to obtain an adhesive exhibiting good adhesion to a polyolefin resin. Also disclosed is a use of such a polyol composition. Specifically disclosed is a polyol composition for polyolefin adhesives, which contains a combination of (A) a terminally hydroxylated conjugated diene polymer having not less than 50% by mole of 1,2-bond unit in a molecule, which is in a liquid state at room temperature, and (B) a terminally hydroxylated conjugated diene polymer having more than 50% by mole of 1,4-bond unit in a molecule, which is in a liquid state at room temperature. Also specifically disclosed are an adhesive for polyolefin, a sealing material for polyolefin and a coating material for polyolefin, each containing the polyol composition and a polyisocyanate curing agent.

Description

Specification

Polyol composition for polyolefin adhesive and use thereof

Technical field

[0001] The present invention relates to a polyol composition for a polyolefin adhesive, and a polyolefin adhesive, a polyolefin sealing material, and a polyolefin coating using the polyol composition.

Background art

[0002] Polyolefin-based materials are used in various fields including the automobile field, the home appliance field, the packaging field, and the building material field. Since the polyolefin resin, which is the main component of the polyolefin resin, cannot be bonded with ordinary adhesives, the development of special adhesives for polyolefin resins has been actively studied. However, an adhesive having sufficient adhesion performance has not been obtained, and when a polyolefin-based material is adhered, the adhesion performance is improved by treating the surface with a primer or an electron beam. . On the other hand, many studies have been made on polyolefin adhesives using mainly hydroxyl-terminated polybutadienes having 1,2 bond units, mainly hydroxyl-terminated polybutadienes having 1,4 bond units, and hydrogenated products thereof. However, there are few adhesives using a mixture of these hydroxyl-terminated polybutadienes.

For example, Patent Document 1 discloses a hydrogenated polybutadiene glycol that is polymerized mainly at 1,4 bonds at room temperature and a liquid polybutadiene glycol that is polymerized mainly at 1,2 bonds at room temperature. A curing agent composition with improved low-temperature stability is disclosed. However, the hydrogenated material that is solid at room temperature has a low cohesive force after curing and low wettability at the adhesive interface, and thus cannot provide sufficient adhesive strength. In addition, the example of Patent Document 1 shows the creep characteristics of adhesion. To improve the low temperature characteristics, the addition of the above-mentioned liquid hydrogenated solution tends to lower the creep characteristics. It is shown.

Patent Documents 2 to 6 disclose compounds containing 1, 2 bond units and 1, 4 bond units in various proportions as polyolefin adhesives or vulcanized rubber adhesives. But However, in any of Patent Documents 2 to 6, the ratio of the 1,2 bond units to the 1,4 bond units is the ratio of the bond units randomly included in one polymer chain. Such mixtures are not shown in these examples, as well as mixtures of diene polymers with diene polymers having 1,4 bond units. In addition, compounds other than the diene polymer such as thermoplastic polyurethane chloroprene rubber are essential components. Furthermore, the hydrogenated compounds used in Patent Documents 2 to 6 are all solid at room temperature. In this respect, the present invention is different from the techniques disclosed in Patent Documents 2 to 6.

[0003] Patent Document 1: Japanese Patent Laid-Open No. 06-158015

Patent Document 2: Japanese Patent Laid-Open No. 54-127928

Patent Document 3: Japanese Patent Laid-Open No. 58-196227

Patent Document 4: Japanese Patent Laid-Open No. 03-170580

Patent Document 5: Japanese Patent Laid-Open No. 03-247684

Patent Document 6: Japanese Patent Laid-Open No. 01-108286

Disclosure of the invention

Problems to be solved by the invention

[0004] The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel polyol composition that provides an adhesive having good adhesion to a polyolefin resin, and uses of the polyol composition. It is.

Means for solving the problem

As a result of extensive research, the present inventors have found that the above object can be achieved by a polyol composition containing a combination of specific liquid conjugated diene polymers. The present invention has been completed based on such knowledge.

That is, the present invention provides the following polyol composition for polyolefin adhesive, and a polyolefin adhesive, a polyolefin sealing material, and a polyolefin coating using the polyol composition.

1. (A) Hydroxyl-terminated conjugated diene polymer having 1,2 bond units in the molecule at 50 mol% or more at room temperature, and (B) Liquid at room temperature having 1,4 bond units in the molecule exceeding 50 mol%. A polyol composition for polyolefin adhesives, comprising a combination comprising a hydroxyl group-terminated conjugated diene polymer.

2. The polyol composition for a polyolefin adhesive as described in 1 above, wherein the polyol composition is a hydrogenated liquid polyol at room temperature, at least one of the hydroxyl-terminated conjugated diene polymers of component (A) and component (B).

3. The polyol composition for a polyolefin adhesive according to the above 1 or 2, which is at least one of the hydroxyl-terminated conjugated diene polymers of component (A) and component (B), S, hydroxyl-terminated polybutadiene or hydroxyl-terminated polyisoprene. .

4. A polyolefin adhesive comprising the polyol composition according to any one of 1 to 3 above and a polyisocyanate curing agent.

5. A polyolefin sealing material comprising the polyol composition according to any one of 1 to 3 above and a polyisocyanate curing agent.

6. A polyolefin paint comprising the polyol composition according to any one of 1 to 3 above and a polyisocyanate curing agent.

The invention's effect

[0006] According to the present invention, it is possible to obtain a polyol composition for polyolefin adhesive that can remarkably improve the adhesion to a polyolefin resin, including a combination of this polyol composition and a polyisocyanate curing agent. Adhesives, sealants, paints and adhesives are excellent in adhesion to polyolefin resins.

BEST MODE FOR CARRYING OUT THE INVENTION

[0007] The polyol composition for polyolefin adhesives of the present invention (hereinafter sometimes simply referred to as "polyol composition") is (A) at room temperature having 1 or 2 bond units of 50 mol% or more in the molecule. A liquid hydroxyl-terminated conjugated diene polymer (hereinafter sometimes abbreviated as “1, 2-THPCD”) and (B) a hydroxyl group which is liquid at room temperature and has more than 50 mol% of 1,4-bond units in the molecule. It includes a combination consisting of an end conjugated diene polymer (hereinafter sometimes abbreviated as “1, 4-THPCD”). Here, room temperature means around 25 ° C.

In the polio yarn yarn and composite of the present invention, 1,2-THPCD and 1,4-THPCD must be liquid at room temperature. Of these! /, One or both of them at room temperature When it is solid, the adhesive strength of the adhesive containing the polyol composition of the present invention as a blending component to the polyolefin resin is significantly reduced.

[0008] In 1,2-THPCD of component (A), the content of 1,2-bond units in the molecule is 50 mol% or more, but from the viewpoint of rubber elasticity and adhesive strength, it is preferably 55- It is 95 mol%, particularly preferably 55 to 75 mol%.

In addition, in component (B) 1, 4 THPCD, the content of 1, 4 bond units in the molecule is 50 mol% or more, strength S, adhesion to polyolefin resins, and hydrogenated compounds at room temperature. from the viewpoint, preferably 60 to 95 mole ^_0/0, particularly preferably 70 to 90 mole ^_0/0

Yes

In the polyol yarn composition of the present invention, the mixing ratio of 1,2-THPCD and 1,4 THPCD is usually about 99:;! To 1:99, preferably 90:10 to mass ratio. 10:90, particularly preferably 80:20 to 20:80. The appropriate mixing ratio varies depending on the type of adherend, but if the ratio of 1, 2 THPCD and 1, 4 THPCD is appropriate, 1, 2— in the cured product of the polyol composition of the present invention. Since the ratio of THPCD and 1 and 4 THPCD block structural units is appropriate, sufficient adhesion can be obtained.

[0010] In the polyol yarn composition of the present invention, a hydrogenated compound obtained by hydrogenating one or both of 1,2-THPCD and 1,4THPCD can be used. Since hydrogenated compounds have higher olefin properties than non-hydrogenated compounds, the use of hydrogenated compounds improves wettability with polyolefin resins and provides excellent adhesion. In particular, a hydrogenated compound of a hydroxyl-terminated polyisoprene is preferable because it has a low crystallinity and easily becomes a liquid at room temperature. Furthermore, the hydrogenated compound is excellent in heat resistance, weather resistance, electrical properties and the like. On the other hand, it is necessary to perform a hydrogenation reaction at a high pressure for the production of a hydrogenated compound, and the production method is complicated and expensive. Therefore, it is preferable to use an unhydrogenated compound from the viewpoint of economy. .

In the polyester yarn of the present invention, at least one of 1, 2-THPCD and 1,4-THPCD, S is preferably a hydroxyl-terminated polybutadiene or a hydroxyl-terminated polyisoprene. Polybutadiene is preferred. Also, a butadiene polyisoprene copolymer or a mixture of hydroxyl-terminated conjugated diene polymers can be used. In the case of hydrogenated compounds, polyisoprene tends to become liquid at room temperature with low crystallinity. Therefore, it is preferable.

[0011] The polyol composition of the present invention includes 1, 2-THPCD and 1, 4-T for the purpose of improving physical properties, lowering viscosity, reducing costs, and other purposes within the range not impairing the effects of the present invention. Other polyols other than HPCD can be blended. Although there is no restriction | limiting in particular as another polyol, It is preferable that compatibility with 1, 2 THPCD and 1, 4 THPCD is favorable. Examples of other polyols that can be used include polyester polyols and polyether polyols. In the polyol composition of the present invention, the content of the other polyol is usually 20% by mass or less, preferably 10% by mass or less based on the polyol composition. If the content of other polyols is large, the water resistance, moisture resistance, electrical properties, etc. may deteriorate. In addition, the 1,2-THPCD and 1,4-TF PCD of the present invention contain other copolymerizable monomer units such as styrene, ethylene, propylene, etc., as long as the characteristics are not impaired. Yo!

[0012] As the hydroxyl-terminated conjugated diene polymer which is liquid at room temperature used in the present invention, a commercially available hydroxyl group-terminated conjugated diene polymer or a polymer produced by a known method can be used. In order to produce this hydroxyl-terminated conjugated diene polymer, for example, one or two or more kinds selected from a gen monomer having 4 to 22 carbon atoms (butadiene, isoprene, black-opened plane, 1,3-pentagene, cyclopentagen, etc.) Hydrogen peroxide, a azo compound having a hydroxyl group (for example, 2,2, -azobis [2-methyl-N- (2-hydroxylethyl) propionamide, etc.) or a peroxide having a hydroxyl group (for example, cyclohexanone peroxide) A radical polymerization method can be employed as the polymerization initiator The amount of the polymerization initiator used is about 1.0 to 50 parts by mass of hydrogen peroxide per 100 parts by mass of Genmonomer, 2, 2, Monoazobis [2 methyl 1 N- (2 hydroxylethyl) propionamide] is 5.0-; about 100 parts by mass, cyclohexanone peroxide De is 5.0 ~; is about 100 parts by weight.

The above polymerization is preferably carried out in a solvent from the viewpoints of force S that can be carried out without a solvent, ease of control of the reaction, and the like. As the solvent, ethanol, isopropanol, n-butanol and the like are usually used. The reaction temperature is about 80 to 150 ° C, and the reaction time is about 0.5 to 15 hours. [0013] The hydroxyl-terminated conjugated diene polymer that is liquid at room temperature used in the present invention is produced by anionic polymerization of a gen monomer similar to the above using a catalyst such as naphthalene dilithium, and further a monoepoxy. It can also be obtained by reacting a compound or the like. Although the polymerization can be carried out without a solvent, it is preferably carried out in a solvent from the same viewpoint as in the case of radical polymerization. As the solvent, saturated hydrocarbons such as hexane and cyclohexane are used. The reaction temperature is 50 to about 100 ° C, and the reaction time is about! To 10 hours. In addition, two or more types of gen monomers may be mixed and used in the polymerization, and an addition polymerizable monomer having 2 to 22 carbon atoms may be added at a ratio of 50 mol% or less based on the gen monomer. Good.

Examples of the addition-polymerizable monomer having 2 to 22 carbon atoms include butene, pentene, styrene, α-methylstyrene, acrylonitrile, acrylic acid and its ester, methacrylic acid and its ester, butyl chloride, butyl acetate and acrylamide.

After completion of the above reaction, the solvent is distilled under reduced pressure to remove the solvent, unreacted monomers and the like, thereby obtaining a hydroxyl group-terminated conjugated diene polymer.

[0014] Generally, when the former radical polymerization method is used, a compound mainly containing 1,4 bond units is obtained, whereas when the latter anion polymerization method is used, mainly 1, 2 bond units are included. A compound is obtained.

The number average molecular weight of the hydroxyl-terminated conjugated diene polymer used in the polyol composition of the present invention is usually 300 to about 10,000, preferably <is 500 to 5,000, and the hydroxyl group content is usually 0.2 to 10 meq. / g, preferably (approx. 0.5 to 5 meq / g, particularly preferable (approx. 0.7 to 2 meq / g. In addition to the molecular end, the hydroxyl group can also be present inside the molecular chain. .

[0015] The present invention also provides a polyolefin adhesive, a polyolefin sealing material, and a polyolefin coating comprising the polyol composition and a polyisocyanate curing agent. The polyolefin adhesive, polyolefin sealing material and polyolefin coating of the present invention are liquid polymer compositions.

The polyisocyanate compound used as the curing agent is not particularly limited, but is selected in consideration of reactivity, safety, cost, and physical properties of the resulting cured product. As the polyisocyanate compound, a pre-synthesized by separately reacting polyol and polyisocyanate. Polymers can also be used.

The polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule, and is a reactive isocyanate group that reacts with the hydroxyl group of the liquid hydroxyl-terminated conjugated diene polymer or its hydrogenated compound. It is what has. Examples of the polyisocyanate compound include ordinary aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

[0016] Specifically, for example, 4,4'-diphenylmethane diisocyanate, a mixture of 2,2, -diphenylmethane diisocyanate (all MDI), tolylene diisocyanate (TDI), Carpositimide-modified diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, phenylene diisocyanate, naphthalene 1,5-diisocyanate, o toluidine diisocyanate, triphenylmethane triisocyanate, tris ( And aromatic polyisocyanates such as isocyanatophenyl) thiophosphate and isopropylbenzene 2,4 diisocyanate.

[0017] Also, aliphatic-aromatic polyisocyanates such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI) (isocyanate groups are not directly bonded to the aromatic ring. And a polyisocyanate bonded to an aromatic ring via an aliphatic group.

Hexamethylene diisocyanate, dodecane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4 Examples thereof include aliphatic polyisocyanates such as isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, and trimethylhexamethylene diisocyanate.

In addition, transcyclohexane 1,4-diisocyanate, bicycloheptanetriisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), hydrogenated trimethylate. Examples thereof include alicyclic polyisocyanates such as range isocyanate, hydrogenated xylylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate. [0018] In addition, cyclized trimers (isocyanurate-modified products) of the above polyisocyanate compounds, biuret metamorphosis, ethylene glycol, 1,4 butanediol, propylene glycol, dipropylene glycol, trimethylone Propane, polyetherol polyol monoole, polymer polyol, polytetramethylene ether glycol, polyester polyol, attalinole polyol, polyalkadiene polyol, polyalkadiene polyol hydride, partially crosslinked ethylene acetate butyl copolymer, castor An addition reaction product of a polyol compound such as an oil-based polyol and the polyisocyanate compound is used.

These polyisocyanate compounds can also be used as a mixture of two or more. Furthermore, the isocyanate groups of these polyisocyanate compounds can be used as phenols, oximes, imides, mercaptans, alcohols, ε A so-called blocked isocyanate compound blocked with a blocking agent such as force prolatatam, ethyleneimine, α-pidonidone, jetyl malonate, sodium bisulfite, boric acid or the like can also be used.

The amount of polyisocyanate used is usually such an amount that NCO / OH (molar ratio) is 0.5 to 2.5, preferably 0.8 to 1.5.

[0019] The liquid polymer composition, which is the polyolefin adhesive, polyolefin sealing material or polyolefin coating of the present invention, has improved adhesiveness and other physical properties, improved processability due to reduced viscosity, heat resistance, weather resistance, etc. Known additives can be added to improve the chemical resistance and chemical resistance. Examples of such additives include inorganic fillers, organic fillers, antioxidants, ultraviolet anti-aging agents, antistatic agents and other stabilizers, extenders for reducing costs, and colorants such as pigments and dyes. , Plasticizers, process oils and bituminous substances.

By adding an inorganic filler to the liquid polymer composition, the adhesion to polyolefin resin is significantly improved. Inorganic fillers include zinc, aluminum, copper, nickel, glass spheres, glass flakes, glass fibers, carbon black (channel black, furnace black, acetylene black, thermal black), carbon fibers, graphite, and brass. Vest, kaolin clay, wax stone clay, talc, cassiteite, cryolite, keystone, diatomaceous earth, slate powder, whiting, feldspar powder, my strength, gypsum, quartz powder, fine silica, attapulgite, seri Site, volcanic ash, meteorite, silica, alumina, zinc oxide, magnesium oxide , Zirconium oxide, titanium oxide, iron oxide, molybdenum dioxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, zeolite, potassium titanate, boron nitride, boron nitrite and disulfide Examples include molybdenum. Calcium carbonate is especially preferred as an inorganic filler! /

Yes

[0020] Examples of organic fillers include rubber powder, cellulose, lignin, chitin, leather powder, coconut shell, wood powder, cotton, hemp, wool, silk, and other natural fibers, nylon, polyester, vinylon, and acetate. , Synthetic fibers such as acrylic, polyethylene resin, polypropylene resin, polystyrene resin, acrylonitrile butadiene styrene resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polymethylmethacrylate resin, polychlorinated butyl resin, epoxy resin, It is possible to list powders or granules of synthetic resin such as phenol resin.

The blending amount of these inorganic fillers and organic fillers is not particularly limited, but is usually 500 parts by mass or less, preferably 200 parts by mass or less with respect to 100 parts by mass of the polyol composition of the present invention.

[0021] The liquid polymer composition containing the polyol composition and the polyisocyanate curing agent is prepared by blending the above components in the above proportions. In preparing this liquid polymer composition, using a mixing device, a kneading device, etc., usually 0 to about 120 ° C., preferably about 15 to 100 ° C. for about 0.5 seconds to 8 hours. The mixture is preferably stirred and mixed for 1 second to 5 hours. For the preparation of the liquid polymer, a method called a one-shot method or a method called a prepolymer method is usually used.

In the one-shot method, first, at least the components other than the polyisocyanate compound are blended and mixed at the above temperature and time to obtain a mixture. The polyisocyanate compound and additive components not used in the previous mixing are added to this mixture and mixed at the above temperature and time to obtain a liquid polymer composition. The preferred NCO / OH (molar ratio) in this liquid polymer composition is 0.5-5.

[0022] The prepolymer method includes the following prepolymer method (1) and prepolymer method (2). In the prepolymer method (1), NCO / OH, NCO / NH or NCO / (OH + NH) is 1 · 7 to 2 5 (equivalent ratio), preferably in the range of 1.7 to 5.5, at least one of the hydroxyl-terminated conjugated diene polymer and the polyamine compound is reacted with the polyisocyanate compound to obtain a prepolymer. This reaction may be performed in the presence of some or all of the other compounding components, or may be performed in the absence of the other compounding components. The reaction temperature is usually 0 to about 120 ° C, preferably 15 to 100 ° C, and the reaction time is usually about 0 .;! To about 10 hours, preferably 0.5 to 8 as described above. It's time. The remaining blending components are mixed with this prepolymer at the same temperature and reaction time as described above to obtain a liquid polymer composition.

[0023] In the prepolymer method (2), NCO / OH, NCO / NH, or NCO / (OH + NH2) is in the range of 1 · 7 to 5 · 0 (equivalent ratio), and all components are mixed and reacted. To get a prebolimer. The reaction temperature is the same as in the prebolimer method (1), and the time is usually from 0.;! To 10 hours, preferably from 0.5 to 8 hours. By reacting this prepolymer with moisture (water) in the air, a liquid polymer composition is obtained.

The liquid polymer composition thus prepared is used in various applications including polyolefin adhesives, polyolefin sealing materials, and olefin coatings, and cured in various forms. give.

Example

[0024] Next, the force S for explaining the present invention in more detail by way of examples, and the present invention is not limited to these examples! /.

Example 1

Hydroxyl-terminated polybutadiene polyol (manufactured by Idemitsu Kosan Co., Ltd., Poly bd R-45HT; containing 1,4 bonds in 80 mol%, in liquid form) and hydroxyl-terminated polybutadiene polyol (manufactured by Sartoma, Inc. 2 bonds (containing 65 mol%, liquid) was mixed at a mass ratio of 75:25. Add diphenylmethane diisocyanate (125M made by Nippon Polyurethane Industry Co., Ltd.) as a polyisocyanate-based curing agent to NCO / OH (molar ratio) to 1.05, and mix with stirring. Thereafter, dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd.) was added as a reaction catalyst at a mass ratio of 0.01 to prepare a liquid adhesive composition. As an adherent, the above adhesive was applied to two PP plates (Prime Polymer Co., Ltd., J-6083HP) 3 mm thick, 25 mm wide, and 100 mm long, with the surface wiped with isopropyl alcohol. The composition was applied and overlaid. In this state, after curing for 72 hours in an environment of 25 ° C and 60% humidity, a universal tensile testing machine (Tensilon manufactured by A & D Co., Ltd.) The tensile shear bond strength (JIS Κ6848: 1999 and JIS K6850: 1999ί) was measured and found to be 0 · 57 MPa.

[0025] Example 2

In Example 1, instead of hydroxyl-terminated polybutadiene polyol (manufactured by Idemitsu Kosan Co., Ltd., Poly bd R-45HT; 1,4 bond content 80 mol%, liquid), hydrogenated polyisoprene polyol Ltd., EPOL; l, 4-linkage content 80 mol ^_0/0, liquid) used, this EPOL a hydroxyl terminated polybutadiene polyol (US Satoma one company Ltd., KRASOL- LBH- P 2000; 1, 2 bond content of 65 mol%, The adhesive composition was prepared in the same manner as in Example 1 except that the liquid composition was used at a mass ratio of 50:50. The tensile shear bond strength was measured by the same method as in Example 1. As a result, it was 0.71 MPa.

[0026] Example 3

In Example 2, EPOL and KRASOL were used instead of KRASOL-LBH-P2000 using hydroxyl-terminated hydrogenated polybutadiene polyol (Karta-Surma Co., Ltd., KRASOL-HLBH-P2000; 1, 2 bond content: 65 monole, liquid). —HLBH— An adhesive composition was prepared in the same manner as in Example 2 except that P2000 was used at a mass ratio of 25:75. The tensile shear bond strength was measured in the same manner as in Example 1. As a result, it was 0.777 MPa.

[0027] Example 4

In Example 1, except that 100 parts by mass of calcium carbonate (Shiraishi Kogyo Co., Ltd., Shirakaba CCR) was added to 100 parts by mass of Poly bd R—45HT and KRASOL—LBH—P2000. An adhesive composition was prepared in the same manner as in Example 1. The tensile shear bond strength was measured in the same manner as in Example 1. As a result, it was 1. OOMPa.

[0028] Comparative Examples 1 and 2

In Example 1, the adhesive composition was prepared in the same manner as in Example 1 except that only one of Poly bd R—45HT and KRASOL LBH—P2000 was used and the NCO / OH (molar ratio) was set to 1 · 05. Produced. Attempts were made to measure tensile shear bond strength in the same manner as in Example 1. I got it.

[0029] Comparative Example 3

In Example 3, adhesion was carried out in the same manner as in Example 3 except that hydrogenated polybutadiene polyol (manufactured by Mitsubishi Chemical Corporation, polytail H; 1, 4 bond content 80 mol%, solid) was used instead of EPOL. An agent composition was prepared. The tensile shear bond strength was measured by the same method as in Example 1. As a result, it was 0.29.

The above examples and comparative examples are summarized in the following table.

[0030] [Table 1]

LBH: KRAS0L-LBH-P20OO HLBH: RASOL-HLBH-P2000

Industrial applicability

The polyol composition for polyolefin adhesives of the present invention and the liquid polymer composition containing an isocyanate curing agent are used in various applications including polyolefin adhesives, polyolefin sealing materials and polyolefin coatings. The cured product can be cured in various forms.

Claims

The scope of the claims

[1] (A) Hydroxyl-terminated diene polymer having 1,2 bonding units in the molecule at 50 mol% or more at room temperature and (B) normal temperature having more than 50 mol% of 1,4 bonding units in the molecule A polyol composition for polyolefin adhesives, comprising a combination comprising a liquid hydroxyl-terminated conjugated diene polymer.

[2] The polyol composition for a polyolefin adhesive according to claim 1, wherein the polyol composition is a liquid polyol at room temperature which is hydrogenated at least one of the hydroxyl group-terminated conjugated diene polymers of the component (A) and the component (B).

[3] At least one of the hydroxyl group-terminated conjugated diene polymers of the component (A) and the component (B) is a hydroxyl-terminated polybutadiene or a hydroxyl-terminated polyisoprene.

2. The polyol composition for polyolefin adhesives according to 2.

[4] A polyolefin adhesive comprising the polyol composition according to any one of claims 1 to 3 and a polyisocyanate curing agent.

[5] A polyolefin sealing material comprising the polyol composition according to any one of claims 1 to 3 and a polyisocyanate curing agent.

[6] A polyolefin paint comprising the polyol composition according to any one of claims 1 to 3 and a polyisocyanate curing agent.