JP3448691B2 - Urethane resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a urethane resin composition.

[0002]

2. Description of the Related Art Solventless urethane resins having excellent adhesiveness to hydrophobic materials such as plastic have not been found yet. Furthermore, it is a one-liquid solvent-free type that exhibits excellent adhesiveness to a wide range of plastics from polar polymer materials such as polyvinyl chloride to non-polar polymer materials such as polyolefin resins such as polyethylene and polypropylene. No urethane resin has been found. Therefore, a so-called solvent-based urethane resin obtained by solution polymerization or dilution of an urethane resin with an organic solvent is provided for adhesion of difficult-to-adhere materials such as plastics.

Generally, a solvent-based urethane resin is much more adhesive than a solventless adhesive because the organic solvent contained partially dissolves the surface of a hydrophobic substance such as a plastic material or gives an affinity. It is advantageous. However, even such a solvent-based urethane resin is not capable of adhering to a wide range of plastics, and the reality is that the solvent and urethane resin are selected according to the type and properties of the plastic. In addition, when considering adhesion, if it is a solventless type, it is necessary for the urethane resin itself, which is a polymer in a liquefied state, to have a direct affinity for various plastics at the initial stage of adhesion. Since good wetting cannot be obtained with the resin, the adhesion range tends to be inevitably limited. Therefore, there is no solvent-free urethane resin that has excellent adhesiveness at room temperature in plastics called difficult-to-bond materials, and there is no choice but to use solvent-based urethane resin that is dangerous and harmful and causes environmental pollution. It was continuing.

In order to solve such a situation, a urethane resin composition called urethane hot melt has been proposed as a part of a solventless type. All of these resin compositions show a solid state at room temperature, the urethane-based resin itself liquefied by heating and melting becomes a thermally active state, and the adherend is also improved after warming the adherend and the surface energy of both is increased. In order to activate, a high affinity for each other can be obtained. However, such a resin composition cannot be effectively adhered to any of various plastics in a wide range from polar polymer materials to non-polar polymer materials. Moreover, when adhesion is carried out using such a resin composition, the polyisocyanate contained in the composition is volatilized into the atmosphere by heating, and as a result, a new hazard or environmental pollution such as generation of harmful vapor or mist is generated. Will be invited. Therefore, the hot melt type urethane resin composition cannot solve the drawbacks of the solvent type urethane resin.

[0005]

In view of such a situation, the present inventors have proposed a solventless type for any of a wide range of plastics ranging from polar polymer materials to nonpolar polymer materials at room temperature. The inventors have earnestly conducted research to develop a urethane resin composition that can exhibit excellent adhesiveness and adhesion and does not have the above-mentioned drawbacks of solvent-based urethane resins.

[0006] First, the present inventors roughly divided the world's difficult-to-bond plastic materials into two groups. Polyvinyl chloride (hereinafter "PVC") is used to evaluate the adhesiveness and adhesion.
,) ABS resin, nylon, polyester, nitrocellulose, and other films, sheets, plates, and other highly polar plastic materials are used as the polar polymer group, and the polyethylene foam is sliced to form untreated polyethylene on the surface. Exposed material (hereinafter referred to as "untreated PE foam"), JIS 6768 polyethylene polypropylene wetting test method, wetting index 36d
Polyethylene film showing yn / cm, 34 dyn /
A non-polar polymer group includes a polypropylene film having a cm and a plastic material having low polarity such as an ethylene / propylene / diene-based material (hereinafter referred to as “EPDM”).
Hereinafter, the former is abbreviated as a polar polymer group and the latter is abbreviated as a non-polar polymer group, and unless otherwise specified, the test materials used in the following adhesion test are referred to as such.

The necessary condition for adhesion is to keep the adherend sufficiently wet, and therefore it is necessary to keep the liquid state at the beginning of the adhesion. However, in the present invention, in order to avoid liquefaction due to unnecessary heating, it should be kept at room temperature. The condition was that it showed a liquid state and was applied as it was so that the bonding work could be performed. As a polyol component for obtaining such a liquid urethane resin, the present inventors have conducted various studies on three kinds of polyether polyol, polyester polyol and hydroxyl group-terminated polybutadiene.

Polyoxyalkylene polyol (hereinafter referred to as "PPG") which is a representative of polyether polyol
Reacts with excess polyisocyanate to easily give a liquid urethane resin called an NCO-terminated prepolymer, which is easily resinified by moisture in the air. However, the prepolymer of PPG and polyisocyanate was poor in adhesiveness and could not sufficiently adhere all selected test materials, and easily peeled off due to the interfacial peeling phenomenon. Therefore, it was found that the polyether polyol is inconvenient as a polyol component for obtaining a desired liquid urethane resin.

Since the polyester polyol has an ester bond in the molecule, it can be expected to give affinity to the polar polymer group. This polyester polyol can obtain a prepolymer which becomes solid at room temperature and becomes liquid by reaction with excess polyisocyanate. Using this liquid prepolymer, the test materials of the two groups of the polar polymer group and the nonpolar polymer group were adhered, and although some adhesive effects were observed in the polar polymer group, the overall Was not enough for. All of the non-polar polymers had poor adhesiveness and were easily peeled off due to an interfacial peeling phenomenon. Therefore, it was found that polyester polyol is also inconvenient as a polyol component for obtaining a desired liquid urethane resin.

Since hydroxyl group-terminated polybutadiene (hereinafter referred to as "polybutadiene glycol") has a molecular structure similar to that of polyolefin, it can be expected to give affinity to a nonpolar polymer group. This polybutadiene glycol is a liquid compound having hydroxyl groups at both ends of polybutadiene. This compound may be polymerized at the 1,4 position or the 1,2 position of the conjugated double bond of butadiene as a starting material, and thus various isomers are produced as polybutadiene. That is, when 1,4-addition polymerization of butadiene occurs, cis-1,4 bond polybutadiene glycol and trans-1,4 bond polybutadiene glycol are produced (hereinafter, these are collectively referred to as "1,4 adduct"). On the other hand, when polymerized at the 1,2 position, three types of stereoisomers of 1,2-bond syndiotactic polybutadiene glycol, 1,2-bond isotactic polybutadiene glycol and 1,2-bond atactic polybutadiene glycol are produced ( Hereinafter, these are collectively referred to as "1,2 adducts". Conventionally, polybutadiene glycol has been used in the form of a mixture of these isomers and / or in the same molecule, a moiety based on 1,4 addition polymerization such as cis-1,4 bond, trans-1,4 bond, etc.
It is commercially available in the state of coexisting with a part based on addition polymerization. Therefore, in the present invention, regardless of the origin of the mixture or the fine structure in the same molecule, a type containing more than 50% by weight of the portion based on the 1,4 adduct is referred to as "1,4-PBG". , A type containing 50% by weight or more of a portion based on a 1,2 adduct in the whole is "1,2-
PBG ". A liquid prepolymer can be easily obtained from these polybutadiene glycols by reacting with excess polyisocyanate. Thus, two types of prepolymers using 1,4-PBG or 1,2-PBG as the polyol component were used to bond the test materials of the two groups of the polar polymer group and the nonpolar polymer group. Although some of the non-polar polymers had an adhesive effect, the overall prepolymer was inadequate. All of the polar polymers had poor adhesiveness and were easily peeled off due to an interfacial peeling phenomenon. Therefore, polybutadiene glycol (1,4-PB
G and 1,2-PBG) were also found to be inconvenient as a polyol component for obtaining the desired liquid urethane resin.

Next, polyester polyol and 1,4-
PBG was mixed and this mixed polyol was reacted with excess polyisocyanate to obtain a prepolymer. Also,
Mixing polyester polyol and 1,2-PBG,
This mixed polyol was reacted with excess polyisocyanate to obtain a prepolymer. When these prepolymers were used to bond the test materials of the two groups of the polar polymer group and the nonpolar polymer group, any of the prepolymers had poor adhesion to all the test materials, and the interfacial peeling phenomenon occurred. It was easily peeled off. Further, these prepolymers were phase-separated into two phases within a few days and had extremely poor compatibility. From these, as a result of the poor compatibility of the above prepolymer, as compared with the prepolymer synthesized by using polyester polyol and polybutadiene glycol alone as the polyol component, the width of adhesiveness is reduced, and the offsetting effect is expressed. Can be interpreted as

Further, a polyether polyol, a polyester polyol and 1,4-PBG were mixed, and this mixed polyol was reacted with an excess of polyisocyanate to obtain a prepolymer. Further, a polyether polyol, a polyester polyol and 1,2-PBG were mixed, and this mixed polyol was reacted with an excess of polyisocyanate to obtain a prepolymer. These prepolymers are
All were excellent in compatibility. And using these prepolymers, the test materials of two groups of the polar polymer group and the non-polar polymer group were adhered,
Got amazing findings. That is, the prepolymer in which 1,4-PBG was incorporated into a part of the polyol component had poor adhesiveness to all test materials and easily peeled off due to the interfacial peeling phenomenon. The prepolymer in which PBG was incorporated as a part of the polyol component was able to exhibit excellent adhesion to all test materials. Even if the polyether polyol itself has poor adhesiveness, it acts as a compatibilizing agent for the polyester polyol, 1,4-PBG or 1,2-PBG, so that the compatibility of the obtained prepolymer is improved and Polyol and 1,4-PB
It is understandable that the original adhesive function of G or 1,2-PBG can be restored. However, in polybutadiene glycol, 1,4-PBG and 1,2-PB formed from the same starting material butadiene
It is noteworthy that, of the G, the former has poor adhesion to all test materials despite having improved compatibility, and the latter exhibits excellent adhesion to all test materials. is there.

The present invention has been completed based on these findings.

That is, the present invention provides (A) polyether polyol, (B) polyester polyol and (C) 1,
The present invention relates to a urethane resin composition containing a urethane resin composed of a mixed polyol composed of 2-PBG and a polyisocyanate.

As the polyether polyol used as the component (A) in the present invention, conventionally known polyether polyols are widely used as long as they have two or more hydroxyl groups at the molecular ends and ether bonds in the molecule. For example, polyoxyalkylene diol (specifically, polyoxyethylene glycol, polyoxypropylene glycol,
Such as polyoxybutylene glycol and copolymers thereof, polyoxyalkylene triols (specifically, those obtained by addition-polymerizing ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. with glycerin, trimethylolpropane, etc.), etc. Examples thereof include polyoxyalkylene polyol; polyoxytetramethyl glycol obtained by ring-opening polymerization of tetrahydrofuran, and the like. In the present invention, these are used alone or in combination of two or more. Of the above polyether polyols, other polyols (B) component and (C)
Considering the compatibility with the components and the prepolymer, a polyether polyol having a number average molecular weight of 1000 to 10000 is preferable, and a polyether polyol having a number average molecular weight of 2000 to 6000 is particularly preferable. Among the above polyether polyols, polyoxyalkylene polyols are preferable.

As the polyester polyol used as the component (B) in the present invention, as long as it is a compound having a hydroxyl group at the terminal having an ester bond as a repeating unit, a conventionally known one can be widely used. For example, a polycarboxylic acid ( Condensed polyester polyol obtained mainly by dehydration condensation of adipic acid or phthalic acid) and a polyhydric alcohol (specifically glycol, triol, etc.); Lactone polyester polyol obtained by ring-opening polymerization of ε-caprolactone; Polycarbonate diol obtained by phosgenation or transesterification with diphenylene carbonate; Polyester polyol by polyaddition reaction of polycarboxylic acid anhydride and diepoxide; Reaction between acid chloride and alkali salt of hydroxy compound Polyester polyol according to; urethane-modified polyester polyols, such as by introducing a urethane group or the like within the molecule, and the like. In the present invention, these are used alone or in combination of two or more. Among the above polyester polyols, in order to obtain a low-viscosity prepolymer or to exhibit excellent adhesiveness to various plastic materials, polyhydric alcohols such as diethylene glycol, hexyl glycol, neopentyl glycol and adipic acid, sebacine A condensation-type polyester polyol obtained by a condensation reaction with a polyvalent carboxylic acid such as acid, isophthalic acid and trimellitic acid,
A normal-temperature liquid polyol having a number average molecular weight of 300 to 10,000 is suitable. In order to impart even higher adhesion performance, it is desirable to use, as the polyester polyol, one obtained by introducing an aromatic polyvalent carboxylic acid such as isophthalic acid into a part of the condensed polyester polyol.

The 1,2-PBG used as the component (C) in the present invention is a hydroxyl group-terminated polybutadiene having a molecular structure of 1,2 adduct as a main component as described above.
1,2-PBG is obtained by adding ethylene oxide to both ends of a butadiene oligomer obtained by various methods such as anion living polymerization of butadiene, polymerization using a palladium-based or molybdenum-based transition metal catalyst, and Na polymerization. Manufactured. At this time, the 1,4 adduct is produced as a by-product together with the 1,2 adduct, but the 1,2 adduct in 1,2-PBG
As long as the content of the adduct is 50% by weight or more, the intended effect of the present invention is exhibited. In the present invention, 1,2-PBG
Since the higher the content of the 1,2 adduct in the composition is, the more excellent the adhesive performance is, the content of the 1,2 adduct in the 1,2-PBG is preferably 70% by weight or more. The 1,2-PBG used in the present invention is, for example, NISSO-PBG-1000, NISSO- from Nippon Soda Co., Ltd.
Commercially available under the trade names of PBG-2000 and NISSO-PBG-3000. The 1,2-PBG used in the present invention may be hydrogenated. Such 1,2-PBG is commercially available, for example, from Nippon Soda Co., Ltd. under the conditions of NISSO-PB GI-1000, NISS.
O-PB GI-2000, NISSO-PBGI-3
It is marketed under the trade name such as 000. On the other hand, 1,4-P
BG is Polybd R4 from Idemitsu Petrochemical Co., Ltd.
Although it is marketed under the trade name of 5-HT, Polybd R15-HT, etc., the content of 1,2 adduct contained in the mixed PBG of 1,4-PBG and 1,2-PBG is 50% by weight. Within the above range, such 1,4-PBG
It is needless to say that the desired effects of the present invention can be exhibited even if the above is used in combination with 1,2-PBG.

The chemical structure of the 1,2 adduct is represented by the following chemical formula.

[0019]

[Chemical 1]

In the above structure, syndiotactic,
Although there are stereotactic types such as isotactic and atactic types that do not have regularity, in the present invention,
An atactic type that does not give regularity is particularly preferable because it gives wider adhesiveness.

In the present invention, a mixture of the above components (A), (B) and (C) is used as the polyol component. The mixing ratio of these components is not particularly limited, but usually 5 to 200 parts by weight of the component (B) and 5 to 200 parts by weight of the component (C) per 100 parts by weight of the component (A). Is good. If the blending amount of the component (B) is less than 5 parts by weight, the adhesiveness to polar polymers such as PVC decreases, and if it exceeds 200 parts by weight, the adhesiveness to non-polar polymers such as polyolefins decreases and at the same time it is liquid at room temperature. Is not preferable because it may not be retained and may be solidified. On the other hand, if the compounding amount of the component (C) is less than 5 parts by weight, the adhesion to the non-polar polymer will be poor, and if it exceeds 200 parts by weight, the adhesion to the polar polymer will be poor and at the same time the compatibility will be poor and phase separation may occur. So
Not preferable. In the present invention, 20 to 120 parts by weight of the component (B) and 2 parts of the component (C) are used per 100 parts by weight of the component (A).
It is particularly preferable to add 0 to 120 parts by weight.

The polyisocyanate used in the present invention is a compound having two or more isocyanate groups in one molecule, a so-called polyfunctional isocyanate compound. As such a polyfunctional isocyanate compound, conventionally known compounds can be widely used, and for example, toluylene diisocyanate (hereinafter referred to as “TDI”), 4,4′-diphenylmethane diisocyanate (hereinafter referred to as “MDI”), hexamethylene diisocyanate (hereinafter referred to as “MDI”). "HMDI"), xylylene diisocyanate (hereinafter "XDI"), meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate,
Isocyanate compounds such as hydrogenated xylylene diisocyanate and isophorone diisocyanate; Sumidule N
Buret polyisocyanate compound such as (Sumitomo Bayer Urethane Co.); Polyisocyanate having isocyanurate ring such as Desmodur IL, HL (Bayer AG), Coronate EH (Nippon Polyurethane Industry Co., Ltd.) Examples of the compound include adduct polyisocyanate compounds such as Sumidule L (manufactured by Sumitomo Bayer Urethane Co., Ltd.) and Coronate HL (manufactured by Nippon Polyurethane Industry Co., Ltd.). In the present invention, these are used alone or in combination of two or more. Among the above polyisocyanates, in order to exhibit excellent adhesiveness to various plastic materials, MDI,
It is preferable to use TDI or HMDI.

The urethane resin of the present invention is obtained by reacting the mixed polyol with polyisocyanate. The urethane resin of the present invention also includes a urethane prepolymer. There is no particular limitation in producing the urethane resin, and the urethane resin may be produced from the mixed polyol and the polyisocyanate according to a conventionally known method. Usually, the simplest method of obtaining a liquid resin at room temperature is to mix components (A), (B) and (C) in predetermined amounts, and allow polyisocyanate to act on them.
It is a method for producing a urethane resin. Further, a so-called two-component type use method is also possible in which the mixed polyol of the component (A) and the component (B) is reacted with polyisocyanate to synthesize an NCO-terminated urethane prepolymer, and the component (C) is allowed to act on it. is there. The point is that a urethane resin composed of three types of polyol components and polyisocyanate may be used. Further, in producing the urethane resin, various additives such as a catalyst and a stabilizer may be added at any stage before the reaction, during the reaction and after the reaction.

Further, in the urethane resin composition of the present invention, plasticizers, high-boiling solvents, thermoplastic polymers, tackifying resins, coupling agents, antioxidants, ultraviolet absorbers, white pigments such as titanium white, various types, etc. Fillers such as coloring pigments, dyes, calcium carbonate, carbon black, clay, talc and the like can be appropriately blended according to the use and purpose.

[0025]

【The invention's effect】

(1) The urethane resin composition of the present invention can give excellent adhesiveness and adhesion to a plastic material which is said to have poor adhesion in the absence of a solvent and in a room temperature range. Here, the difficult-to-adhesive plastic material is PV
It is a wide range of materials from polar polymers such as C, ABS resin, polyester, nylon and nitrocellulose to non-polar polymers such as polyethylene, polypropylene and EPDM. In particular, polyethylene includes untreated polyethylene foam that has not been surface-treated, such as the sliced surface of polyethylene foam. For polyethylene and polypropylene films, refer to "JIS
6768 polyethylene-polypropylene wetting test method "shows a wetting index of 34 to 36 dyn / c.
Room temperature adhesion is possible even in the range of m.

(2) An adhesive obtained by using the urethane resin composition of the present invention has excellent heat resistance, heat creep resistance and
Exhibits durability such as water resistance, boiling resistance, and chemical resistance.

(3) Since the urethane resin composition of the present invention is solvent-free and can be used in the normal temperature range, there is no problem of environmental pollution of the solvent, and there is no harmful isocyanate vapor or mist generated by heat bonding. Occurrence can be suppressed to a minimum.

(4) The urethane resin composition of the present invention is
Even the urethane resin using the mixed polyol of the component (A), the component (B) and the component (C) as the polyol component is excellent in compatibility, does not undergo phase separation over time, and does not cause a side reaction. It also has excellent storage stability.

(5) Therefore, the urethane resin composition of the present invention comprises a solventless adhesive, a coating agent such as paint, and the like.
It can be widely used in applications where current solvent-based urethane resins are used.

[0030]

EXAMPLES The present invention will be described more in detail with reference to examples of the present invention, but the present invention is not limited to these examples. In the following, the terms “part” and “%” simply mean “part by weight” and “% by weight” unless otherwise specified.

Example 1 In synthesizing a urethane prepolymer, the following polyols were prepared.

Polyether polyol P1 (polyoxyalkylene polyol, abbreviated as "PPG, P1" hereinafter): number average molecular weight 4900, hydroxyl value 35.3, number of hydroxyl groups per molecule 3, viscosity 850 cps / 25 ° C, commercial product Name Exenol 820 (manufactured by Asahi Glass Co., Ltd.).

Polyester polyol E1 (hereinafter “ fat ”
肪 polyesters, E1 "and abbreviated): diethylene glycol as glycol, hexylene glycol, condensed polyols obtained by esterifying adipic acid polyhydric alcohol neopentyl glycol, hydroxyl value 56.
6, acid value 0.36, number average molecular weight 2000.

Polyester polyol E2 (hereinafter abbreviated as "aromatic polyester, E2"): Diethylene glycol as a glycol, hexylene glycol diol as an aliphatic dicarboxylic acid adipic acid, sebacic acid, and aromatic dicarboxylic acid as an isophthalic acid ester Condensed condensation polyol, hydroxyl value 56.7, acid value 0.22, number average molecular weight 2000.

Polybutadiene glycol B1 (hereinafter abbreviated as "polybutane 1,2, B1"): 1,2-PBG,
Number average molecular weight 1850, content of 1,2 adduct 85% or more, hydroxyl value 53.4, viscosity 14500 cps / 45
C, trade name NISSO-PB G2000 (manufactured by Nippon Soda Co., Ltd.).

Polybutadiene glycol B2 (hereinafter abbreviated as "polybuta-1,4, B2"): 1,4-PBG,
Number average molecular weight 2800, 1,2 adduct content 20% or less, hydroxyl value 50.0, viscosity 5000 cps / 30 ° C.,
Product name Polybd R45-HT, manufactured by Idemitsu Petrochemical.

Various prepolymers were synthesized by carrying out a urethanization reaction using these polyols and MDI (trade name: Sumidule 44S, NCO content: 33.6%, manufactured by Sumitomo Bayer Urethane Co., Ltd.). In the synthesis, the theoretical NCO content and reaction conditions were made common.

[Synthesis Method] A hydroxyl value was previously known in a reactor equipped with a 2-liter four-neck separable flask, a stirrer with a vacuum seal, a reflux tube, a thermometer, a decompression device, and a nitrogen gas flow device. According to the formulation shown in Table 1, a total of 1000 parts of the polyol of
Decompression dehydration is performed under the condition of 00 ° C. It was confirmed that the water content of each blended polyol was 200 ppm or less. Each of the blended polyols that had been dehydrated under reduced pressure by heating was once cooled to 50 ° C., and the NCO content of the synthetic prepolymer was 10.
The necessary amount of MDI was measured so as to be 0%, and MDI was mixed all at once, and then reacted at 80 to 85 ° C. for 4 hours under a nitrogen stream.

After 4 hours, dibutyltin dilaurate (hereinafter abbreviated as "DBTDL") dissolved in dioctyl phthalate was blended in an amount of 0.03 part per 1000 parts of blended polyol in terms of pure DBTDL, After that, aging reaction was carried out at 80 to 85 ° C. for 1 hour under a nitrogen stream, and the NCO content of the prepolymer was theoretical (10.0%).
After confirming the following, it was cooled. After cooling, the cans were collected in a dry and sealable glass bottle and subjected to nitrogen purging to obtain prepolymer samples. The next day, part of the NCO content was measured again, and this was used as the end point NCO content.
The viscosity was also measured and used as the end point viscosity. Furthermore, the storage stability of these prepolymers after being left at 50 ° C. for 1 month was examined. Regarding the storage stability, the compatibility was observed visually by the occurrence of phase separation together with the NCO content and viscosity measurement after the passage of time.

[0040]

[Table 1]

The following adhesion tests were carried out using each of the prepolymers shown in Table 1.

(1) Test Material The adhesion test was carried out at room temperature by a cold press method using the following various plastic materials and plywood.

(A) Polar polymer group; PVC: Semi-rigid PVC sheet (made by Dai Nippon Printing Co., Ltd.) with 0.2 mm thickness and 23 parts of plasticizer with wood grain printing. ABS resin: Beige plate with a thickness of 1 mm (made by Tsutsunaka Plastic Co., Ltd.) 3. Nylon: White plate made of 6.6 nylon with a thickness of 1 mm 4. Polyester: 0.2 mm thick transparent polyethylene terephthalate film (unbonded surface) 5. 5. Nitrocellulose: Milky white nitrocellulose plate (b) nonpolar polymer group having a thickness of 0.5 mm; Polyethylene foam: A foam with polyethylene exposed by slicing with a foaming ratio of 10 times (Mitsufuku board,
Made by Mifuku Industry Co., Ltd. 7. Polyethylene film: translucent polyethylene film having a thickness of 0.15 mm and a wetting index of 36 dyn / cm (JIS 6768) 8. Polypropylene film: Transparent polypropylene film having a thickness of 0.1 mm and a wetting index of 34 dyn / cm (JIS 6768) 9. EPDM plate: black plate having a thickness of 1 mm and having a glossy surface (c) plywood surface white lauan type, 5 pl adjusted to a water content of 9 to 10%
y Plywood (thickness 5.5 mm, type 1, manufactured by Yongdai Sangyo Co., Ltd.).

(2) Adhesion method A bar coater was used to apply a coating amount of 100 to the fiber direction of plywood cut into 30 cm × 15 cm in a thermostatic chamber at 20 ° C. and 65% relative humidity (hereinafter abbreviated as “RH”). ~ 120g /
Apply so that it will be m ² . Immediately after coating, put various plastic materials cut to the same size as the plywood, deaerate with a rubber roll, and stack up within 20 minutes at closed deposition time 20 ° C
Cold press at. Cold press condition is 0.5kg /
The adhesive strength is measured after unifying at 16 cm ² for 16 hours, curing in the same constant temperature room for about 7 days, and sufficiently curing with moisture.

(3) Method of measuring adhesive strength (normal 90 ° peel test) The adhesive is cut into a width of 25 mm and a length of 10 mm, and a 90 ° peel test is conducted in parallel with the fiber direction of the plywood. 20 tests
The average value of the peel strength is obtained at a pulling rate of 200 mm / min using 5 pieces for each adhesive in a thermostatic chamber at RH of 65%. At this time, importance is attached to the presence or absence of material breakage on the plywood surface layer as well as the adhesive strength. The unit is N / 25 mm. The measuring instrument is Autograph AG5000, manufactured by Shimadzu Corporation.

Evaluation of Adhesion Failure State ◎: Plywood surface layer material breakage is 80% or more and excellent adhesion strength ○: Plywood surface layer material breakage is 50 to 80% or more, good adhesion strength Δ: Plywood surface layer material Fracture of 50% or less, insufficient adhesive strength x: Plywood surface layer material has no fracture and has poor adhesive strength due to interfacial peeling. In addition, in this test, with polyethylene foam, the adhesive strength is the same as the product of the present invention. Therefore, when the polyethylene foam could not be peeled due to the destruction of the base material of the polyethylene foam, it was described as "non-peelable".

The results of the adhesion test are shown in Table 2.

[0048]

[Table 2]

As is clear from Table 2, all the test materials of the present invention have excellent strength, and their fracture state extends to the fracture of the plywood surface layer. On the other hand, in each of the comparative examples, the adhesive strength was poor in all cases, and most of them had interfacial peeling.

Example 2 Under the same synthesis conditions as in Example 1, prepolymers were synthesized according to the formulations shown in Table 3, and a PVC sheet and a non-polar polymer group were represented as representatives of the polar polymer group shown in Example 1. The following test is carried out using polyethylene foam as the material. The test materials and the adhesion conditions are the same as in Example 1.

[0051]

[Table 3]

(1) Adhesion of PVC sheet / plywood (A) Method of measuring adhesive strength (normal 90 degree peel test) By the same method as in Example 1.

(B) 90 ° water-resistant peeling Test pieces having a width of 25 mm and a length of 10 mm were immersed in water at 20 ° C. for 78 hours, and then peeled 90 ° in the same manner as in Example 1 while being wet. There are 5 test pieces, and the unit is N / 25 mm.

(C) Heat-resistant creep test Part of a test piece having a width of 25 mm and a length of 10 mm was peeled off, and 1
Load 500g weight to 90 degree angle at 00 ℃ 1
The peel length after 16 hours is measured. 5 test pieces
The unit is mm / 1 hr and mm / 16 hr. still,
When 50 mm or more is peeled off, the time is described as "entire surface peeling", and the test is finished at that time. Therefore, the higher the value of this test, the worse.

(D) JAS1 type immersion peeling test A test piece (4 pieces) cut into 75 mm square was immersed in boiling water for 4 hours by a special plywood test method according to Japanese Agricultural Standards (hereinafter abbreviated as "JAS"), and then 60 Dried at ℃ for 20 hours,
After again immersing in boiling water for 4 hours, it is dried at 60 ° C. for 3 hours and the test is terminated, and abnormalities (shrinkage, swelling, peeling) of the bonded portion are observed.

◎ There is no abnormality in the adhesive part ○ There is partial shrinkage, swelling, and peeling, but it is within the JAS conformance standard range △ Shrinkage, swelling, and peeling, and does not reach the JAS conformance standard × Shrinkage, Swelling and peeling are noticeable, the JAS conformity standard is not reached, and the adhesive performance is very poor.

(2) Adhesion of polyethylene foam / plywood (e) Measurement of adhesion strength by JAS plane tensile test A 50 mm square test piece is subjected to a plane tensile test with four test pieces using the JAS method. The pulling speed was set to 5 mm / min, and the adhesive strength focused on the strength value and where breakage occurred. The unit is N / cm ² , and the measuring instrument is Autograph AG5000.

⊚: Excellent adhesion strength due to polyethylene foam base material fracture. ○: Good adhesion strength due to partial polyethylene foam fracture and base material peeling. Sufficient x: Peeling at the entire surface interface, poor adhesive strength.

(F) Water resistance JAS Plane tensile test by measuring the adhesive strength The plane tensile test piece prepared in (e) was left in water for 78 hours with the metal plate still attached, and the same as wet (e) Perform a plane tensile test.

(G) JAS1 type immersion peeling test Perform the test as in (d).

The results of these tests are shown in Table 4.

[0062]

[Table 4]

As described above, the product of the present invention was excellent not only in adhesiveness but also in various performances such as heat resistance, water resistance and boiling resistance. On the other hand, in Comparative Example, the adhesiveness and other properties were obviously inferior to those of the product of the present invention, probably because the original adhesiveness was poor.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masahiko Makino 4-7-9 Tsurumi, Tsurumi-ku, Osaka-shi, Osaka Prefecture Konishi Corporation Osaka Research Institute (72) Yuka Suzuki 4-chome, Tsurumi-ku, Osaka-shi, Osaka No. 9 in Osaka Research Institute, Konishi Co., Ltd. (56) Reference JP-A-56-82864 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 18 / 00-18 / 87

Claims (3)

(57) [Claims] 1. An (A) polyether polyol, (B)
Obtained by reacting a polyester polyol and (C) a mixed polyol comprising a hydroxyl group-terminated polybutadiene having a 1,2 adduct as a main component with polyisocyanate
A urethane resin composition containing an NCO-terminated urethane resin. 2. The mixed polyol is 100 parts by weight of component (A).
5 to 200 parts by weight of component (B), component (C) per part by weight
The urethane resin according to claim 1, containing 5 to 200 parts by weight of
Composition. 3. The mixed polyol is 100 parts by weight of component (A).
20 to 120 parts by weight of the component (B) and (C)
The urethane according to claim 1, which contains 20 to 120 parts by weight.
Resin composition.