WO2023157979A1

WO2023157979A1 - Curable resin composition and hot melt adhesive

Info

Publication number: WO2023157979A1
Application number: PCT/JP2023/006208
Authority: WO
Inventors: 憲人吉野; 珠世佐々井
Original assignee: 東洋紡株式会社
Priority date: 2022-02-21
Filing date: 2023-02-21
Publication date: 2023-08-24

Abstract

The present invention provides a curable resin composition that has good handling properties in a low-temperature molten state and high flexibility and, after curing reaction, shows excellent adhesive strength and thermal creep resistance at room and high temperatures. This curable resin composition, which contains a modified polyolefin A, a polyolefin B and an organic polymer C, is characterized in that; the modified polyolefin A is a polymer obtained by graft polymerization of a polyolefin polymer a with a compound having a moisture-curing functional group; the softening point of the polyolefin polymer a is 80°C or higher and lower than 120°C; the softening point of the polyolefin B is 120-170°C inclusive; the glass transition temperature of the organic polymer C is -35°C or lower; and the organic polymer C is incompatible with the modified polyolefin A and the polyolefin B.

Description

Curable resin composition and hot melt adhesive

The present invention relates to curable resin compositions and hot melt adhesives.

　Conventionally, hot-melt adhesives have been used in fields such as building materials, automotive interior materials, and electrical component assembly because they can be adhered in a short period of time and do not contain solvents.

For example, automobile interior materials (ceilings, doors, seats, etc.) consist of molded products and surface materials. Polyolefin molded articles (polypropylene, polyethylene, etc.) are mainly used as the molded articles, and polyolefin skin materials are mainly used as the skin materials. Automobile interior materials are manufactured by adhering these moldings and skin materials with a hot-melt adhesive using a press crimping method, a vacuum forming method, or the like.

Curable resin compositions are widely used as materials for hot-melt adhesives (see, for example, Patent Documents 1 and 2).

Patent Document 1 describes a curable resin composition in which a silane coupling agent is blended with a styrene block copolymer obtained by graft polymerization of an acrylic monomer.

Further, in Patent Document 2, a reaction of a modified polyolefin resin modified with an unsaturated carboxylic acid and/or a derivative thereof and a compound having a functional group and a reactive silyl group reactive with the modified polyolefin resin is disclosed. A curable resin composition comprising the product is described.

Japanese Patent Application Laid-Open No. 2000-303047 Japanese Patent Application Laid-Open No. 2010-059319

However, the curable resin composition described in Patent Document 1 has poor handling properties in a low-temperature molten state, so there is a problem that coating is difficult.

In addition, the curable resin composition described in Patent Document 2 has a problem of poor heat-resistant creep resistance.

In recent years, from the viewpoint of production efficiency, curable resin compositions that have good handling properties even in a low-temperature molten state, are highly flexible, and have excellent adhesive strength at room temperature and high temperature after the curing reaction and heat creep resistance have been used. A hot melt adhesive is desired. However, the curable resin compositions disclosed in Patent Documents 1 and 2 do not have these desired properties.

The present invention has been made in view of the above. An object of the present invention is to provide a resin composition.

As a result of intensive studies to achieve the above object, the inventors of the present invention have found that the following method improves the handling property in a low-temperature molten state, so that the coating work can be easily performed, the flexibility is high, and the curing reaction is completed. The inventors have found that a curable resin composition which is excellent in adhesive strength and heat resistant creep property even in a high temperature environment and which can achieve both heat resistant creep property and flexibility can be obtained, and have completed the present invention.

That is, the present invention consists of the following configurations.
Section 1.
containing modified polyolefin A, polyolefin B and organic polymer C,
The modified polyolefin A is a polymer obtained by graft-polymerizing a compound having a moisture-curable functional group to the polyolefin polymer a,
The softening point of the polyolefin polymer a is 80° C. or more and less than 120° C.,
The softening point of the polyolefin B is 120° C. or higher and 170° C. or lower,
The glass transition point of the organic polymer C is −35° C. or lower,
The curable resin composition, wherein the organic polymer C is incompatible with the modified polyolefin A and the polyolefin B.
Section 2.
Item 2. The curable resin composition according to Item 1, wherein the polyolefin B is a polymer obtained by graft-polymerizing a compound having a moisture-curable functional group to the polyolefin polymer b.
Item 3.
Item 3. The curable resin composition according to Item 1 or 2, wherein the organic polymer C has a moisture-curable functional group.
Section 4.
Item 4. The curable resin composition according to any one of Items 1 to 3, wherein the mass ratio of the modified polyolefin A and the polyolefin B is 90:10 to 60:40.
Item 5.
Item 5. The curability according to any one of items 1 to 4, wherein the mass ratio of the total amount of the modified polyolefin A and the polyolefin B to the organic polymer C is 95:5 to 75:25. Resin composition.
Item 6.
A hot melt adhesive comprising the curable resin composition according to any one of items 1 to 5.

The curable resin composition of the present invention has good handling properties in a low-temperature molten state, is rich in flexibility, has adhesive strength in room temperature and high-temperature environments after the curing reaction, and has sufficient heat-resistant creep properties.

FIG. 2 is a diagram showing an adhesive sample in a method for evaluating heat-resistant creep resistance. FIG. 3 is a diagram showing the relationship between a measurement sample and a weight in the method for evaluating heat-resistant creep resistance.

The curable resin composition that is an embodiment of the present invention will be described below. Although the description of the constituent elements described below may be made based on representative embodiments and specific examples, the present invention is not limited to such embodiments.

As used herein, room temperature means a temperature within the range of 20°C to 25°C.

As used herein, high temperature means a temperature within the range of 80°C to 200°C.

In this specification, the low-temperature melting state means a state of melting at a low temperature that does not affect the base material, and means a temperature within the range of 120°C to 140°C.

The curable resin composition contains modified polyolefin A, polyolefin B and organic polymer C as essential components. The modified polyolefin A is a polymer obtained by graft-polymerizing a moisture-curable functional group to the polyolefin polymer a.

<Polyolefin polymer>
Polyolefin polymers include, for example, ethylene, propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, α-olefin homopolymers polymerized from monomer components such as 1-octadecene and 1-eicosene; ethylene-propylene copolymers, ethylene-propylene-butylene copolymers, ethylene-propylene-isobutylene copolymers, etc. Copolymers of α-olefins other than ethylene and ethylene; α-olefins and other monomers copolymerizable with α-olefins (e.g., butadiene, 1,4-hexadiene, 7-methyl-1,6 - conjugated or non-conjugated dienes such as octadiene, 1,8-nonadiene and 1,9-decadiene; cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, norbornene and dicyclopentadiene); polychloroprene; polyisoprene; copolymers of isoprene or butadiene with acrylonitrile and/or styrene; and polybutadiene. In the present invention, among the polyolefin polymers described above, propylene homopolymers, ethylene-propylene copolymers, ethylene-propylene-butylene copolymers, and ethylene-propylene-isobutylene copolymers are preferred, and propylene homopolymers are more preferred. .

In the present invention, the polyolefin polymer is preferably amorphous or low-crystalline polyolefin. For example, propylene polymers, ethylene-propylene copolymers, ethylene-propylene-butylene copolymers, and ethylene-propylene-isobutylene copolymers are preferred.

In this specification, amorphous or low-crystalline polyolefin means that the crystallization energy (J/g) by differential scanning calorimetry is 50 J/g or less. The crystallization energy was obtained by heating the sample from 20° C. to 230° C. using a differential scanning calorimeter, cooling it to −100° C., and then reheating the sample to 230° C. at 10° C./min. Let it be the amount of heat absorbed.

In the present invention, two types of polyolefin polymers (polyolefin polymer a and polyolefin polymer b) having different softening points are used as the polyolefin polymers. Polyolefin polymer a and polyolefin polymer b may each be a single polyolefin polymer, or two or more polyolefin polymers may be mixed in an arbitrary ratio and used.

The softening point of the polyolefin polymer a is 80 to less than 120°C, preferably 80 to 100°C, more preferably 80 to 95°C. When the softening point of the polyolefin polymer a is 80° C. or higher, the curing reaction of the curable resin composition and the hot-melt adhesive using the curable resin composition after cooling and solidification is accelerated, which is preferable. When the softening point of the polyolefin polymer a is less than 120° C., the curable resin composition and the hot-melt adhesive using the curable resin composition can be easily applied to an adherend.

The softening point of the polyolefin polymer b is 120°C to 170°C, preferably 140°C to 160°C, more preferably 150°C to 160°C. When the softening point of the polyolefin polymer b is 120° C. or higher, the curing reaction after cooling and solidification of the curable resin composition and the hot-melt adhesive using the curable resin composition is accelerated and cured under any environment. The curable resin composition and the hot-melt adhesive using the curable resin composition are improved in adhesive strength under room temperature and high temperature environments and in heat resistant creep properties. When the softening point of the polyolefin polymer b is 170° C. or lower, the curable resin composition and the hot-melt adhesive using the curable resin composition can be easily applied to an adherend. In the present invention, the softening point of the polyolefin polymer refers to a value measured according to JIS K6863 Hot Melt Adhesive Softening Point Test Method.

The melt viscosity of the polyolefin polymer a at 190°C is preferably 15,000 mPa·s or less, more preferably 14,000 mPa·s, and most preferably 12,000 mPa·s. When the melt viscosity of the polyolefin polymer a at 190° C. is 15000 mPa·s or less, the curable resin composition and the hot melt adhesive using the curable resin composition can be easily applied to an adherend. be able to. The melt viscosity of the polyolefin polymer a at 190° C. is a value measured according to the JIS K6862 hot-melt adhesive melt viscosity test method.

The method for producing the polyolefin polymer is not particularly limited, and a wide range of known methods can be employed, including solution polymerization, slurry polymerization, gas phase polymerization, and the like. Catalysts are usually used in these polymerization methods, and examples of such catalysts include catalysts containing zirconium compounds and the like, metallocene catalysts, and the like. The conditions for each polymerization reaction are the state of the catalyst used (homogeneous or heterogeneous (supported type)), the production method (solution polymerization method, slurry polymerization method, gas phase polymerization method), and the characteristics of the target polymer. Alternatively, it can be appropriately set according to the form of the polymer. The solution polymerization method is described, for example, in JP-A-53-134889 and Japanese Patent No. 5064662. In Examples described later, polyolefin polymers were produced based on the solution polymerization method.

In the case of the above solution polymerization method or slurry polymerization method, an organic solvent or olefin itself can be used as a medium. Organic solvents used in the above solution polymerization method or slurry polymerization method include aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, octane, decane, and dodecane; cyclopentane, methylcyclopentane, cyclohexane, and the like. aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as dichloromethane, chloroethane, 1,2-dichloroethane and chlorobenzene. These organic solvents can be used alone or in combination of two or more. Among these organic solvents, aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, octane, decane and dodecane are preferred, and heptane is more preferred.

Also, an impurity remover for increasing the productivity of the polyolefin polymer may be added to the polymerization reaction system together with the catalyst. Examples of the impurity remover include triethylaluminum. The amount of the catalyst is not particularly limited, but the central metal concentration of the catalyst in the reaction system used for polymerization is preferably 10 ^-8 to 10 mol/L, more preferably 10 ^-7 to 10 ^-2 mol/L. is more preferable.

The polymerization temperature in the polymerization of the polyolefin polymer can be appropriately selected depending on the reactants, reaction conditions, and the like. For example, in the case of solution polymerization, the polymerization temperature is preferably 0 to 250°C, more preferably 10 to 200°C. In the case of slurry polymerization method or gas phase polymerization method, the polymerization temperature is preferably 0 to 120°C, more preferably 20 to 110°C.

The polymerization pressure in the method for producing a polyolefin polymer is preferably normal pressure to 20 MPa, more preferably normal pressure to 10 MPa. Polymerization of the polyolefin polymer can be carried out batchwise, semicontinuously or continuously. The molecular weight and molecular weight distribution of the final polymer produced according to the above polymerization method can be adjusted by adjusting the polymerization temperature or by injecting hydrogen into the reactor.

In the present invention, the polyolefin polymer is preferably produced by polymerizing single or two or more olefin monomers using a solution polymerization method in the presence of a metallocene catalyst. An activator and/or a scavenger (trapping agent) may be added during polymerization. The olefin monomers include ethylene, propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, α-olefins such as 1-octadecene and 1-eicosene; conjugated or non-conjugated dienes such as butadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene and 1,9-decadiene; Cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, norbornene, dicyclopentadiene and the like can be preferably used.

Examples of the metallocene catalyst include bis(cyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, bis(ethylcyclopentadienyl)zirconium dichloride, bis(iso-propylcyclopentadienyl) Zirconium dichloride, bis(n-propylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(t-butylcyclopentadienyl)zirconium dichloride, bis(thexylcyclopentadienyl) ) zirconium dichloride, bis(trimethylsilylcyclopentadienyl)zirconium dichloride, bis(trimethylsilylmethylcyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium chlorohydride, bis(cyclopentadienyl)methylzirconium chloride, bis (Cyclopentadienyl)ethylzirconium chloride, bis(cyclopentadienyl)methoxyzirconium chloride, bis(cyclopentadienyl)phenylzirconium chloride, bis(cyclopentadienyl)dimethylzirconium, bis(cyclopentadienyl)diphenyl Zirconium, bis(cyclopentadienyl)dineopentylzirconium, bis(cyclopentadienyl)dihydrozirconium, bis(cyclopentadienyl)dimethoxyzirconium, bis(cyclopentadienyl)zirconium dichloride, trichloro(indenyl)titanium ( IV), trichloro(cyclopentadienyl)titanium(IV), bis(cyclopentadienyl)zirconium chloride hydride, hafnocene dichloride, bis(butylcyclopentadienyl)zirconium(IV) dichloride, bis(propylcyclopenta) dienyl)hafnium (IV) dichloride, trichloro(pentamethylcyclopentadienyl)titanium (IV), μ-chlorobis(η5-cyclopentadienyl)(dimethylaluminum)-μ-methylenetitanium, bis(pentamethylcyclopenta) dienyl)zirconium (IV) dichloride, bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)dimethyltitanium and the like. Among these metallocene catalysts, bis(t-butylcyclopentadienyl)zirconium dichloride is preferred in the present invention. These metallocene catalysts can be used alone or in combination of two or more.

<Modified Polyolefin A>
The modified polyolefin A in the present invention is a polymer obtained by graft-polymerizing a compound having a moisture-curable functional group to the polyolefin polymer a.

Modified polyolefin A is preferably 0.5 to 10 parts by mass (more preferably 0.75 to 8 parts by mass, more preferably 0.75 to 8 parts by mass) of a compound having a moisture-curable functional group with respect to 100 parts by mass of polyolefin polymer a. Preferably 1 to 5 parts by mass) is a polymer obtained by graft polymerization.

In the present invention, the compound having a moisture-curable functional group is preferably a hydrolyzable silane compound having an ethylenically unsaturated group.

The modified polyolefin A is preferably a silane-modified polyolefin polymer. The silane-modified polyolefin polymer is a polymer obtained by graft-polymerizing a hydrolyzable silane compound having an ethylenically unsaturated group to polyolefin polymer a.

In the present invention, moisture-curable functional groups include hydrolyzable silyl groups and isocyanate groups. A hydrolyzable silyl group is preferred from the viewpoint of reactivity control.

<Hydrolyzable silyl group>
In the present invention, the modified polyolefin A usually has at least one or more (preferably two or more) crosslinkable hydrolyzable silyl groups. Examples of the hydrolyzable silyl group include -Si(OR ¹ ) _n R ² _3-n (wherein R ¹ and R ² are the same or different and are an alkyl group having 1 to 5 carbon atoms or an alkyl group having 6 to 20 carbon atoms). and n is an integer of 1 to 3). The alkyl group having 1 to 5 carbon atoms means a linear or branched alkyl group having 1 to 5 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group. , isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group and the like. Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, naphthyl group, indenyl group and anthryl group. An alkoxysilyl group is preferred as the hydrolyzable silyl group. Alkoxysilyl groups include monoalkoxysilyl, dialkoxysilyl, and trialkoxysilyl groups. The monoalkoxysilyl group includes a dimethylmethoxysilyl group and a dimethylethoxysilyl group. The dialkoxysilyl group includes a methyldiethoxysilyl group. The trialkoxysilyl group includes a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group and a triphenoxysilyl group.

<Polyolefin B>
The polyolefin B in the present invention may be a polymer (obtained by graft polymerization) obtained by graft-polymerizing a compound having a moisture-curable functional group to the polyolefin-based polymer b. may be used without modification. That is, polyolefin B may be polyolefin polymer b. Polyolefin B is preferably a polymer obtained by graft-polymerizing a compound having a moisture-curable functional group. In that case, the components described in <Modified polyolefin A> and <Hydrolyzable silyl group> can be used.

The softening point of polyolefin B is 120°C to 170°C, preferably 140°C to 160°C, more preferably 150°C to 160°C. When the softening point of polyolefin B is 120° C. or higher, the curing reaction after cooling and solidification of the curable resin composition and the hot-melt adhesive using the curable resin composition is accelerated, and the curability is cured under any environment. The resin composition and the hot melt adhesive using the curable resin composition are improved in adhesive strength in room temperature and high temperature environments and in heat resistant creep properties. When the softening point of polyolefin B is 170° C. or lower, the curable resin composition and the hot-melt adhesive using the curable resin composition can be easily applied to an adherend. In the present invention, the softening point of polyolefin B refers to a value measured according to JIS K6863 Hot Melt Adhesive Softening Point Test Method.

It is preferable that the melt viscosities of the polyolefin polymer a and the polyolefin B in a 190° C. environment satisfy the following relational expression i.
Melt viscosity of polyolefin polymer a>melt viscosity of polyolefin B i
In this case, the curable resin composition and the hot-melt adhesive using the curable resin composition can be easily applied to the adherend.

<Polymer obtained by graft polymerization of a compound having a moisture-curable functional group>
In the present invention, the polymer obtained by graft-polymerizing a compound having a moisture-curable functional group is, for example, a polyolefin polymer that generates radicals with a radical initiator and is graft-polymerized with a compound having a moisture-curable functional group. can be obtained by When the polyolefin B is a polymer obtained by graft polymerization of a compound having a moisture-curable functional group, the polyolefin polymer a and the polyolefin polymer b are mixed in advance, and the mixture is added with the moisture-curable functional group. It may be obtained by graft polymerization with a compound having a group, or the polyolefin polymer a and the polyolefin polymer b may be individually graft-polymerized with a compound having a moisture-curable functional group and then mixed. good.

When the polyolefin polymer a and the polyolefin polymer b are mixed in advance, the mass ratio of the polyolefin polymer a and the polyolefin polymer b in the mixture is: polyolefin polymer a:polyolefin weight Combined b=6:4 to 9:1 is preferred, and 6.5:3.5 to 8.5:1.5 is more preferred. When the mass ratio of polyolefin polymer a to polyolefin polymer b is polyolefin polymer a:polyolefin polymer b=6:4 to 9:1, under a temperature environment below the softening point of polyolefin B , it exhibits a constant melt viscosity for a long period of time, and the curable resin composition and the hot-melt adhesive using the curable resin composition can be easily applied to an adherend. In addition, the curable resin composition cured under any environment and the hot-melt adhesive using the curable resin composition are improved in adhesive strength under room temperature and high temperature environments and heat resistant creep properties.

The melt viscosity at 140°C of the polymer obtained by graft polymerization of a compound having a moisture-curable functional group is preferably 50,000 mPa·s or less, more preferably 40,000 mPa·s, and most preferably 35,000 mPa·s. In this case, the curable resin composition and the hot-melt adhesive using the curable resin composition can be easily applied to the adherend. The melt viscosity of the curable resin at 140°C is a value measured according to JIS K6862, a method for testing the melt viscosity of hot melt adhesives.

The softening point of the polymer obtained by graft polymerization of a compound having a moisture-curable functional group is preferably 70 to 180°C, more preferably 80 to 170°C, and particularly preferably 90 to 160°C. When the softening point is 70° C. or higher, the curing reaction of the curable resin composition and the hot-melt adhesive using the curable resin composition is accelerated after solidification by cooling, which is preferable. When the softening point is 180° C. or lower, the curable resin composition and the hot-melt adhesive using the curable resin composition can be easily applied to an adherend. The softening point of a polymer obtained by graft-polymerizing a compound having a moisture-curable functional group is a value measured according to JIS K6863 Hot Melt Adhesive Softening Point Test Method.

A polymer obtained by graft polymerization of a compound having a moisture-curable functional group preferably has a low molecular weight component of 2.5 wt % or less when extracted with acetone. Adhesive strength and heat-resistant creep properties of a curable resin composition cured under an arbitrary environment when the low-molecular-weight component is 2.5 wt% or less, and a hot-melt adhesive using the curable resin composition under room temperature and high temperature environments improves.
Here, an acetone extraction method for a curable resin, for example, will be described. An extraction operation using a Soxhlet extractor is performed on the curable resin powdered by freeze-grinding, crystallization or any means. Acetone is used as an extraction solvent. Specifically, it is as follows. (1) A curable resin is pulverized using a freeze pulverizer, and 5.0 g is taken. In addition, the initial weight of the flask for collecting the extract is measured. (2) The fractionated modified polyolefin is introduced into a cellulose cylindrical filter paper, and Soxhlet extraction is performed for 2 hours in a 90° C. environment using 110 ml of acetone introduced into a flask for extract recovery. (3) Using an evaporator, evaporate the extract to dryness after 2 hours, and then measure the weight of the flask after the extraction operation. (4) The weight of the flask before and after Soxhlet extraction is measured to determine the amount of low-molecular-weight components that are acetone extracts. By dividing the amount of the low molecular weight component by the amount of the curable resin obtained by Soxhlet extraction, the proportion of the low molecular weight component can be obtained.

<Compound having a moisture-curable functional group>
In the present invention, the compound having a moisture-curable functional group is preferably a hydrolyzable silane compound having an ethylenically unsaturated group (also referred to as "silane-modified monomer having an ethylenically unsaturated group"). A hydrolyzable silane compound having an ethylenically unsaturated group is represented by, for example, the following formula (1)
(X) _n (R) _3-n -Si-Y Formula (1)
is represented by
(In formula (1) above, Y is an ethylenically unsaturated group, X is a hydrolyzable group, R is an alkyl group, and n represents an integer of 1 to 3.)

Examples of hydrolyzable groups in formula (1) above include halogens, alkoxy groups, alkenyloxy groups, acyloxy groups, amino groups, aminooxy groups, oxime groups, and amide groups. A methoxy group is preferable as the alkoxy group. Here, the number of these hydrolyzable groups bonded to one silicon atom is selected from the range of 1, 2 and 3. Moreover, the number of hydrolyzable groups bonded to one silicon atom may be one or plural. Furthermore, a hydrolyzable group and a non-hydrolyzable group may be attached to one silicon atom. As the hydrolyzable group bonded to the silicon group, an alkoxy group (a monoalkoxy group, a dialkoxy group, a trialkoxy group, etc.) is preferable in terms of ease of handling. In the above formula (1), n is preferably 3.

Examples of Y (ethylenically unsaturated group) in the above formula (1) include a vinyl group, an aryl group, an acrylic group, a methacrylic group, and the like.

Vinyltrimethoxysilane, vinyltriethoxysilane, and 3-methacryloxypropyltrimethoxysilane are preferable as the hydrolyzable silane compound having an ethylenically unsaturated group.

<Method for producing a polymer by graft polymerization of a compound having a moisture-curable functional group>
In the present invention, as a method for producing a polymer obtained by graft-polymerizing a compound having a moisture-curable functional group, a wide range of known methods can be employed, and examples thereof include the following methods:
- A method of obtaining a polymer by graft polymerizing a compound having a moisture-curable functional group to a polyolefin polymer in the presence of a radical initiator or by electron beam radiation.
Here, the details of the polyolefin polymer and the compound having a moisture-curable functional group are described in the above <Polyolefin-based polymer> and the above <Compound having a moisture-curable functional group>, respectively, unless otherwise specified. As I did.

The amount of the compound having a moisture-curable functional group when producing a polymer obtained by graft polymerization of the compound having a moisture-curable functional group is 0.5 per 100 parts by mass of the polyolefin polymer. 1 to 10 parts by mass is preferable, 0.75 to 8 parts by mass is more preferable, and 1 to 5 parts by mass is particularly preferable. When the amount of the compound having a moisture-curable functional group is 0.5 parts by mass or more, the graft polymerization reaction proceeds sufficiently to produce a curable resin composition and a hot-melt adhesive using the curable resin composition. The heat creep resistance after curing and the adhesive strength after curing are further improved. When the amount of the compound having a moisture-curable functional group is 10 parts by mass or less, side reactions such as homopolymerization of the compound having a moisture-curable functional group or decomposition reaction of the polyolefin polymer are further suppressed. .

Examples of the radical initiator include dicumyl peroxide, t-butylperoxyisopropyl carbonate, di-t-butylperoxide, t-butylperbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butylperoctoate, methyl ethyl ketone peroxide, 2, 5-dimethyl-2,5-di(t-butylperoxy)hexane, lauryl peroxide, t-butyl peracetate, t-butyl α-cumyl peroxide, di-t-butyl peroxide, di-t-amyl peroxide, t -amyl peroxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, α,α'-bis(t-butylperoxy)-1,3-diisopropylbenzene, α,α' -bis(t-butylperoxy)-1,4-diisopropylbenzene, 2,5-bis(t-butylperoxy)-2,5-dimethylhexane, 2,5-bis(t-butylperoxy)-2,5 -dimethyl-3-hexyne and the like. These radical initiators can be used alone or in combination of two or more. Among these, dicumyl peroxide and t-butylperoxyisopropyl carbonate are preferred.

A compound containing a nitroxy radical can be used when producing a polymer by graft-polymerizing a compound having a moisture-curable functional group. The compound containing a nitroxy radical is not particularly limited as long as it is a compound having a stable nitroxy radical in the molecule. For example, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), N-tert -butyl-N-[a-diethylphosphono-(2,2-dimethylpropyl)]nitoroxide (DEPN), 2,2,d-trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO), N-tert- butyl-N-(1-tert-butyl-2-ethylsulfinyl)propylnitroxide (BESN), 2,2,10,10-tetraethylisoindolin-N-oxyl (TEDIO) and the like. Derivatives of these compounds can also be used. Such nitroxy radical-containing compounds or derivatives thereof may be used alone or in combination of two or more.

The molar ratio of the nitroxy radical (I) in the nitroxy radical-containing compound to the radical (II) generated from the radical initiator is nitroxy radical (I):radical (II)=1:0. 001 to 1:1, more preferably nitroxy radical (I):radical (II)=1:0.01 to 1:0.1. Within this range, decomposition of the polyolefin polymer by radicals generated from the radical initiator can be suppressed, and the compound having a moisture-curable functional group can be efficiently graft-polymerized to the main chain skeleton of the polyolefin polymer. can be done.

<Silane-modified polyolefin polymer>
In the present invention, the polymer obtained by graft-polymerizing a compound having a moisture-curable functional group is preferably a silane-modified polyolefin polymer. The silane-modified polyolefin polymer is a polymer obtained by graft-polymerizing a hydrolyzable silane compound having an ethylenically unsaturated group to a polyolefin polymer.

In the present invention, a method for producing a silane-modified polyolefin polymer includes graft polymerization of a hydrolyzable silane compound having an ethylenically unsaturated group onto a polyolefin polymer in the presence of a radical initiator or by electron beam radiation. There is a method to make Here, the details of the polyolefin-based polymer, the hydrolyzable silane compound having an ethylenically unsaturated group, and the radical initiator are, unless otherwise specified, the <polyolefin-based polymer> and the <moisture-curable functional group>, respectively. and the above <Method for producing a polymer by graft-polymerizing a compound having a moisture-curable functional group>.

As a method for producing the silane-modified polyolefin polymer, a mixture of the polyolefin polymer a and the polyolefin polymer b is mixed in advance, and then a hydrolyzable silane compound having an ethylenically unsaturated group is graft-polymerized. may In this case, modified polyolefin A and polyolefin B may be bonded via a hydrolyzable silane compound having an ethylenically unsaturated group, or may be bonded directly.

The amount of the hydrolyzable silane compound having an ethylenically unsaturated group used in producing the silane-modified polyolefin polymer is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polyolefin polymer. .75 to 8 parts by weight is more preferred, and 1 to 5 parts by weight is particularly preferred. When the amount of the hydrolyzable silane compound having an ethylenically unsaturated group is 0.5 parts by mass or more, the graft polymerization reaction proceeds sufficiently, and the curable resin composition and the curable resin composition are used. The heat-resistant creep resistance after curing and the adhesive strength after curing of the hot-melt adhesive are further improved. If the amount of the hydrolyzable silane compound having an ethylenically unsaturated group is 10 parts by mass or less, side effects such as homopolymerization of the hydrolyzable silane compound having an ethylenically unsaturated group or decomposition reaction of the polyolefin polymer may occur. The reaction is further suppressed.

The amount of the radical initiator when producing the silane-modified polyolefin polymer is preferably 0.5 to 10 parts by mass, more preferably 0.75 to 8 parts by mass, with respect to 100 parts by mass of the polyolefin polymer. 1 to 5 parts by weight is particularly preferred. When the amount of the radical initiator is 0.5 parts by mass or more, the graft reaction proceeds sufficiently, and the curable resin composition cured under an arbitrary environment and the hot-melt adhesive using the curable resin composition are cooled to room temperature and Adhesion strength under high temperature environment and heat resistant creep property are further improved. When the amount of the radical initiator is 10 parts by mass or less, side reactions such as homopolymerization of the hydrolyzable silane compound having an ethylenically unsaturated group or decomposition reaction of the polyolefin polymer are further suppressed.

The mass ratio of the amount of the radical initiator used and the amount of the hydrolyzable silane compound having an ethylenically unsaturated group used in the production of the silane-modified polyolefin polymer (radical initiator: water having an ethylenically unsaturated group) decomposable silane compound) is preferably 1:0.2 to 1:10, more preferably 1:0.4 to 1:5, even more preferably 1:0.6 to 1:2.5. When the mass ratio of the radical initiator to the hydrolyzable silane compound having an ethylenically unsaturated group is within the range of 1:0.2 to 1:10, the hydrolyzable silane compound having an ethylenically unsaturated group A room temperature and high temperature environment for a curable resin composition cured under an arbitrary environment and a hot melt adhesive using the curable resin composition, in which side reactions such as homopolymerization of the polyolefin polymer or the decomposition reaction of the polyolefin polymer are further suppressed. Adhesive strength under the substrate and heat resistant creep properties are further improved.

The graft polymerization reaction can be carried out in any of a molten state, a solution state (liquid state), a solid state and a swollen state. In the present invention, the graft polymerization reaction using a hydrolyzable silane compound having an ethylenically unsaturated group to a polyolefin polymer can be carried out using a wide variety of devices such as twin-screw extruders, single-screw extruders, and brushes. This can be done by using lavender, batch reactors and the like.

<Organic polymer C>
The curable resin composition of the present invention contains organic polymer C as an essential component. Organic polymer C is incompatible with modified polyolefin A and polyolefin B. Examples of the organic polymer C that can be used include hydrocarbon resins (saturated hydrocarbon resins, unsaturated hydrocarbon resins, hydrocarbon resins having a cyclic structure), polyesters, polyurethanes, acrylic resins, and the like. As the organic polymer C, hydrocarbon resins having quaternary carbons, hydrocarbon resins having a cyclic structure, and polyesters are preferred. Moreover, the organic polymer C preferably has a moisture-curable functional group.

The glass transition point (Tg) of the organic polymer C is -35°C or lower. It is preferably -45°C or lower. When the Tg of the organic polymer C is −35° C. or lower, the curable resin composition and the hot-melt adhesive using the curable resin composition have improved flexibility in a low-temperature environment after solidification by cooling. In addition, Tg refers to a value (midpoint glass transition temperature (Tmg)) measured using a differential scanning calorimeter in accordance with JIS K7121.

When the organic polymer C has a moisture-curable functional group, the organic polymer C is preferably a polymer obtained by graft polymerization of a compound having a moisture-curable functional group. It can be obtained by graft polymerizing a compound having a moisture-curable functional group in the presence of a radical initiator or by electron beam radiation. Moreover, the compound having a moisture-curable functional group is preferably a hydrolyzable silane compound having an ethylenically unsaturated group. Here, details of the polymer obtained by graft polymerization of a compound having a moisture-curable functional group, the hydrolyzable silane compound having an ethylenically unsaturated group and the radical initiator, and the production method thereof, unless otherwise specified. , the descriptions of <Compound Having Moisture-Curable Functional Group> and <Method for Producing Polymer by Graft-Polymerizing Compound Having Moisture-Curable Functional Group> can be applied mutatis mutandis.

When the organic polymer C has a moisture-curable functional group, the polyolefin polymer a, the polyolefin polymer b, and the unmodified organic polymer C are mixed in advance, and the mixture is added with the moisture-curable functional group. It may be obtained by graft polymerization depending on the compound having. In this case, the modified polyolefin A, polyolefin B, and organic polymer C may be bonded via a compound having a moisture-curable functional group. Alternatively, the polyolefin polymer a and the unmodified organic polymer C may be mixed in advance, and the mixture may be graft-polymerized with a compound having a moisture-curable functional group. The modified polyolefin A and the organic polymer C may be bonded via a compound having a moisture-curable functional group. Further, the modified polyolefin polymer A and the polyolefin B may be mixed with the organic polymer C.

When the polyolefin polymer a, the polyolefin polymer b and the unmodified organic polymer C are mixed in advance, the total amount of the polyolefin polymer a and the polyolefin polymer b and the unmodified organic polymer C The mass ratio to the modified product is [polyolefin polymer a+polyolefin polymer b]:unmodified organic polymer C=9.5:0.5 to 7.5:2.5, preferably 9.0. : 1.0 to 8.0: 2.0 is more preferable. In this case, the flexibility of the curable resin composition and the hot-melt adhesive using the curable resin composition in a low-temperature environment is improved. In addition, the adhesive strength and heat resistant creep properties of a curable resin cured under an arbitrary environment or a hot-melt adhesive using a curable resin are improved in room temperature and high temperature environments.

<Curable resin composition>
The mass ratio of modified polyolefin A to polyolefin B in the curable resin composition of the present invention is preferably modified polyolefin A:polyolefin B=90:10 to 60:40, more preferably 85:15 to 65:35. In this case, in a temperature environment below the softening point of polyolefin B, not only does it exhibit a constant melt viscosity for a long time, but the curable resin composition and the hot melt adhesive using the curable resin composition adhere to the adherend. Application work can be easily performed. In addition, the curable resin composition cured under any environment and the hot-melt adhesive using the curable resin composition are improved in adhesive strength under room temperature and high temperature environments and heat resistant creep properties.

The mass ratio of the total amount of modified polyolefin A and polyolefin B to the organic polymer C is [modified polyolefin A + polyolefin B]: organic polymer C = 95:5 to 75:25, preferably 90:10. ~80:20 is more preferred. In this case, the flexibility of the curable resin composition and the hot-melt adhesive using the curable resin composition in a low-temperature environment is improved. In addition, the curable resin composition cured under an arbitrary environment and the hot-melt adhesive using the curable resin are improved in adhesive strength under room temperature and high temperature environments and heat resistant creep properties.

Organic polymer C is incompatible with modified polyolefin A and polyolefin B. Incompatible means that in the dynamic viscoelastic behavior of the curable resin composition in which the organic polymer C is blended with the modified polyolefin A and the polyolefin B, the tan δ peak represented by (storage elastic modulus/loss elastic modulus) is 2. It means that more than one is detected. The dynamic viscoelastic behavior can be measured using a dynamic viscoelasticity measuring device under the following conditions. A specific measuring method will be described in Examples described later.
Measurement conditions for dynamic viscoelasticity measurement:
・Temperature: -100 to 150°C
・Frequency: 10Hz
- Heating rate: 4°C/min.

The organic polymer C is not particularly limited as long as it satisfies the glass transition point, the addition amount, and the incompatibility with the modified polyolefin A and the polyolefin B, but in the dynamic viscoelastic behavior of the curable resin composition, It is preferable to select the type of organic polymer C and adjust the amount added so that the absolute value of the temperature difference between the tops of the two tan δ peaks is within the range of 1 to 100 ° C., preferably in the range of 70 ° C to 20 ° C. It is more preferable to select the type of organic polymer C and adjust the amount to be added so as to be within the range. Preferred specific examples of the organic polymer C include a dicyclopentadiene polymer (Trilene (registered trademark) 65 manufactured by Lion Elastomer), polyisobutylene (OPPANOL (registered trademark) B12SFN, B15SFN, N50SF manufactured by BASF), and the like. is given. Moreover, the value of the weight average molecular weight can take values of 50,000, 70,000, 108,000, and 565,000.

<Hansen Solubility Parameter (HSP)>
The Hansen Solubility Parameter is a value used to predict the solubility of a substance. HSP is based on the idea that "two substances with similar intermolecular interactions are more likely to dissolve in each other". HSP means a vector quantity parameter that divides the Hildebrand solubility parameter into three cohesive energy components: the London dispersion force, the inter-dipole force and the hydrogen bonding force. In the present invention, the component corresponding to the London dispersion force of HSP is a dispersion term (hereinafter also referred to as "δd"), the component corresponding to the dipole force is a polar term (hereinafter also referred to as "δp"), hydrogen A component corresponding to the binding force is described as a hydrogen bond term (hereinafter also referred to as “δh”). These three parameters can be regarded as coordinates in a three-dimensional space (Hansen space). When HSPs of two substances are placed in the Hansen space, the closer the distance between the two points, the easier it is to dissolve each other.

Since HSP is a vector quantity, it is known that almost no pure substance has exactly the same value. In addition, a database has been constructed for HSPs of commonly used substances. Therefore, a person skilled in the art can obtain the HSP value of the desired substance by referring to the database.

Even if the HSP value is not registered in the database, a person skilled in the art can calculate the HSP value from its chemical structure by using computer software such as Hansen Solubility Parameters in Practice (HSPiP). can.

In addition, the HSP value can be determined by performing a dissolution test using multiple solvents with known HSP values for substances whose HSP values are not registered, and inputting the obtained solubilities into HSPiP. . In the case of a mixture consisting of a plurality of substances, the HSP value of the mixture is calculated as the sum of the values obtained by multiplying the HSP value of each contained substance by the volume ratio of the substance to the entire mixture.

For HSP, for example, Hiroshi Yamamoto, S. Abbott, C.; M. Hansen, Chemical Industry, March 2010 issue. As for the HSP distance, for example, Hiroshi Yamamoto, S.; Abbott, C.; M. Hansen, Chemical Industry, April 2010 issue.

The HSP values and interaction radii R ₀ herein are based on S.M. Abbott, C.; M. Hansen, Kagaku Kogyo, March 2010 and Hiroshi Yamamoto, S.; Abbott, C.; M. It was determined using the dissolution test method described in Hansen, Kagaku Kogyo, April 2010.
The Hansen solubility parameter of the polyolefin polymer is a value that varies depending on the monomer structure, molecular weight, molecular weight distribution, and crystallinity of the polyolefin.

In the present invention, the distance Ra-b between the HSP value of the polyolefin polymer a and the HSP value of the polyolefin polymer b can be obtained by the following formula. In the following formula (i), δd1, δp1 and δh1 represent the dispersion term, polarization term and hydrogen bond term of the HSP value of polyolefin a, respectively. δd2, δp2 and δh2 represent the dispersion term, polarization term and hydrogen bond term of the HSP value of polyolefin B, respectively.

In the present invention, the relative energy difference (RED) based on the Hansen Solubility Parameter (HSP) value between the polyolefin polymer a and the polyolefin polymer b can be determined by the following formula. In the following formula (ii), R ₀ indicates the interaction radius of polyolefin polymer a, and R _ab is the difference between the HSP value of polyolefin polymer a and the HSP value of polyolefin polymer b. Indicates distance.

Relative energy difference (RED) is an indicator of affinity for a target substance. The RED calculated from the HSP values of the polyolefin polymer a and the polyolefin polymer b and the interaction radius R ₀ of the polyolefin polymer a is preferably 1 or less. If the RED is 1 or less, the polyolefin polymer a and the polyolefin polymer b can be easily dissolved, and a polyolefin having a uniform moisture-curable functional group grafted can be prepared.

<Physical property values of cured product of curable resin composition>
In the present invention, the cured product of the curable resin composition preferably has a storage modulus of 10 ⁴ to 10 ⁶ Pa at 100°C. When the storage modulus is 10 ⁴ to 10 ⁶ Pa, the heat-resistant creep property after aging and the room-temperature peel strength after aging are improved. The cured product can be obtained by curing the curable resin composition of the present invention under conditions of 60° C. and 80% RH for 7 days and then aging it under conditions of 23° C. and 50% RH for 1 day. The storage elastic modulus is a value obtained by measuring the storage elastic modulus at 100° C. by subjecting the obtained cured product to dynamic viscoelasticity measurement under the following measurement conditions using a dynamic viscoelasticity measuring device. A specific measuring method will be described in Examples described later.
Measurement conditions for dynamic viscoelasticity measurement:
・Temperature: -100 to 150°C
・Frequency: 10Hz
- Heating rate: 4°C/min.

<Moisture curing catalyst>
The curable resin composition of the present invention may contain a moisture curing catalyst. The moisture-curable catalyst can accelerate the dehydration condensation reaction of hydrolyzable silyl groups usually contained in a polymer obtained by graft-polymerizing a compound having a moisture-curable functional group to a polyolefin polymer. The details of the hydrolyzable silyl group are as described in <Hydrolyzable silyl group> above, unless otherwise specified. Hydrolyzable silyl groups undergo a dehydration condensation reaction with a curing catalyst in the presence of moisture to form a crosslinked structure. The details of the polyolefin polymer and the compound having a moisture-curable functional group are as described in the above <Polyolefin-based polymer> and the above <Compound having a moisture-curable functional group>, respectively, unless otherwise specified.

Moisture curing catalysts include, for example, organic bases, organic acids, carboxylates of metals (tin, zinc, iron, lead, cobalt, etc.), organic titanates, and the like. These moisture curing catalysts may be used alone or in combination of two or more.

Examples of organic bases include N-dimethylaniline, N,N-dimethyltoluidine, N,N-dimethyl-p-anisidine, P-halogeno-N,N-dimethylaniline, 2-N-dithylanilinoethanol, tertiary amines such as trilaubutylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, N,N-dimethylbenzylamine, N,N,N',N'-tetramethylbutanediamine; be done. These organic bases can be used alone or in combination of two or more.

Examples of organic acids include toluenesulfonic acid, dodecylbenzenesulfonic acid, acetic acid, stearic acid, and maleic acid. These organic acids can be used alone or in combination of two or more.

Examples of carboxylates of metals (tin, zinc, iron, lead, cobalt, etc.) include dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltin dioctate, stannous acetate, octanoic acid, stannous, lead naphthenate, zinc caprylate, cobalt naphthenate and the like. These carboxylates may be used alone or in combination of two or more.

Examples of organic titanates include tetrabutyl titanate, tetrapropoxytitanate, tetraethoxytitanate, tetraamyl titanate, titanium diisopropoxybisethylacetoacetate, diisopropoxybisacetylacetonate, and the like. These organic titanates may be used alone or in combination of two or more.

In the present invention, the moisture curing catalyst includes dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltin dioctate, stannous acetate, stannous octoate, lead naphthenate, zinc caprylate and At least one selected from the group consisting of cobalt naphthenate is preferred, and dibutyltin dilaurate is more preferred.

In the present invention, when a moisture curing catalyst is included, the content of the moisture curing catalyst is preferably 0.0001 to 2.0 parts by mass, more preferably 0.0005 to 1.0 parts by mass with respect to 100 parts by mass of the curable resin composition. is more preferable, and 0.001 to 0.5 parts by mass is particularly preferable. When the amount is 0.0001 to 10.0 parts by mass, the curable resin composition and the hot-melt adhesive using the curable resin composition can be easily applied to an adherend.

<Diluent>
The curable resin composition of the present invention may further contain one or more diluents. Diluents are generally used to reduce the viscosity of the curable resin composition. When the present invention contains a diluent, the content of the diluent in 100% by mass of the curable resin composition is usually less than 50% by mass, preferably less than 40% by mass, more preferably less than 35% by mass. do. Exemplary diluents include white mineral oils (e.g., Kaydol® oil from Witco), and Shellflex® 371 naphthenic oil (from Shell Oil) and Calsol 5550 (from Calumet Lubricants). naphthenic oil) and the like.

<Tackifier>
When the present invention contains a tackifier, the content of the tackifier in 100% by mass of the curable resin composition is usually less than 50% by mass, preferably less than 40% by mass, more preferably less than 35% by mass. . Tackifying resins include aliphatic, cycloaliphatic and aromatic hydrocarbons and modified hydrocarbons and hydrides; terpenes and modified terpenes and hydrides; rosin and rosin derivatives and hydrides thereof; and mixtures thereof but not limited to them. As a tackifier, a wide range of known commercial products can be used, for example, Eastotac (registered trademark) H-100, H-115, H130 and H142, which are partially hydrogenated alicyclic petroleum hydrocarbon resins manufactured by Eastman Chemical Company. Escorez® 5300, 5637 and 5400, and Escorez® 5600 from ExxonMobil Chemical; Wingtack® Extra from Goodyear Chemical; Hercolite® 2100; Zon from Arizona Chemical atac (registered trademark) 105 and 501 Lite.

<Wax>
When the curable resin composition of the present invention contains wax, the content of the tackifier in 100% by mass of the curable resin composition is usually less than 30% by mass, preferably less than 20% by mass, more preferably 15% by mass. %. As the wax, a wide range of known waxes can be used. Oxidized Fischer-Tropsch waxes, functionalized waxes (eg, hydroxystearamide waxes and fatty amide waxes), and the like. It is common in the art to use the terminology "synthetic high melting waxes" to include high density, low molecular weight polyethylene waxes, by-product polyethylene waxes and Fischer-Tropsch waxes.

<Antioxidant>
When the present invention contains an antioxidant, the content of the antioxidant in 100% by mass of the curable resin composition is usually 0.5% by mass or less, preferably 0.2% by mass or less. As antioxidants, known antioxidants can be widely used, for example, hindered phenolic antioxidants (Ciba-Geigy Irganox (registered trademark) 565, 1010 and 1076); agents (Irgafos (registered trademark) 168 manufactured by Ciba-Geigy); Cyanox (registered trademark) LTDP manufactured by Cytec Industries; Ethanox (registered trademark) 1330 manufactured by Albemarle;

<Example>
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.

<Evaluation method>
Evaluations in Examples and Comparative Examples were carried out by the following measurement methods.

1) Measurement of Melt Viscosity of Polyolefin Polymer The melt viscosity (mPa·s) of the polyolefin polymer at 190° C. was measured in accordance with JIS K 6862, Melt Viscosity Test Method for Hot Melt Adhesives.
・Equipment used: Viscometer (model number “RVDT2” manufactured by Brookfield)
・Measurement temperature: 190°C
- Measurement method: The furnace temperature of the viscometer was set to 190°C, and a predetermined amount of a polyolefin polymer sample was weighed into a cup. A cup in which the sample is weighed is placed in the furnace to melt the resin, and a spindle is placed from above. The spindle was rotated and the melt viscosity (mPa·s) was read when the indicated viscosity value became stable. Table 1 shows the measurement results.

2) Measurement of softening point of polyolefin polymer The softening point (°C) of polyolefin was measured according to JIS K6863, Method for testing the softening point of hot melt adhesives.
・Measurement conditions: Temperature increase rate 5°C/min
・Measurement method: Measured according to JIS K 6863. Specifically, a brass ring filled with a sample is held horizontally in an oil bath, a steel ball of a certain weight is placed in the center of the sample, the bath temperature is raised at the above speed, the sample gradually softens, and the steel ball The softening point (°C) was read by the thermometer when it finally reached the bottom plate with a thickness of 25 mm. Table 1 shows the measurement results.

3) Confirmation of Incompatibility Using a spacer of 200 μm, the produced curable resin composition was pressure-formed under conditions of 140° C. and 10 MPa for 30 seconds to prepare a film-formed sample. "SA-302 desktop test press" manufactured by Tester Sangyo Co., Ltd. was used to prepare film samples. After curing the prepared film sample in an environment of 60 ° C. and 80% RH for 7 days, it is aged for 1 day in an environment of 23 ° C. and 50% RH to obtain a cured sheet sample (cured product of the curable resin composition). got A cured sheet sample was cut into a width of 5 mm and a length of 15 mm to prepare a measurement sample. The prepared measurement sample was mounted on a dynamic viscoelasticity measuring device ("DVA-200" manufactured by IT Keisoku Co., Ltd.), and dynamic viscoelasticity was measured under the following measurement conditions. In the dynamic viscoelastic behavior, two or more tan δ peaks represented by (storage modulus/loss modulus) were detected, and the absolute value of the temperature difference between the two peaks was within the range of 70°C to 20°C. If two or more peaks of tan δ are detected, and the absolute value of the temperature difference between the two peaks is 1 ° C or more and less than 20 ° C, or if it is more than 70 ° C and 100 ° C or less, it is incompatible B, C when the number of peaks was less than 2, or when the temperature difference between the two peaks was less than 1°C in absolute value. Evaluation results are shown in Tables 2 to 6.
<Measurement conditions for dynamic viscoelasticity measurement>
・Frequency: 10Hz
・Measurement temperature range: -100°C to 150°C
- Heating rate: 4°C/min.

4) Evaluation of handling property 4-1. Handling Evaluation of coatability The melt viscosity (mPa·s) of the curable resin composition at 140°C was measured according to JIS K 6862, Melt viscosity test method for hot melt adhesives.
・Equipment used: Viscometer (model number “RVDT2” manufactured by Brookfield)
・Measurement temperature: 140°C
- Measurement method: The furnace temperature of the viscometer was set to 140°C, and a predetermined amount of a polyolefin-based polymer sample was weighed into a cup. A cup in which the sample is weighed is placed in the furnace to melt the resin, and a spindle is placed from above. The spindle was rotated and the melt viscosity (mPa·s) was read when the indicated viscosity value became stable.
A curable resin composition with a melt viscosity of 30000 mPa·s or less in an environment of 140° C. was rated A, 50000 mPa·s or less was rated B, and 50001 mPa·s or more was rated C. Evaluation results are shown in Tables 2 to 6.
4-2. Evaluation of handling property and viscosity stability An arbitrary amount of the produced curable resin composition was taken, and in accordance with the melt viscosity test method for hot melt adhesives of JIS K 6862, the above-mentioned (4-1. Handling coatability evaluation), the melt viscosity 1 (mPa·s) at 140°C of the curable resin composition was measured. An arbitrary amount of the produced curable resin composition was introduced into a flask equipped with a reflux tube, and stirred at 120 rpm for 1 hour under an environment of 140°C. An arbitrary amount of the curable resin composition after stirring was taken, and the melt viscosity 2 at 140° C. of the curable resin composition was measured in the same manner as the melt viscosity 1. Regarding melt viscosity 1 and melt viscosity 2 of the curable resin composition, (melt viscosity 2 - melt viscosity 1) ≤ 1500 mPa s is "A", 1500 mPa s < (melt viscosity 2 - melt viscosity 1) ≤ A value of 2000 mPa·s was rated as "B", and a value of 2000 mPa·s<(melt viscosity 2−melt viscosity 1) was rated as "C". Evaluation results are shown in Tables 2 to 6.

5) Evaluation of flexibility (0°C)
Using a spacer of 200 μm, the produced curable resin composition was pressure-formed under conditions of 10 MPa and 30 seconds in an environment of 140° C. to obtain a film-formed sample. A test piece for measurement was prepared by cutting the film-formed sample into a width of 10 mm and a length of 40 mm. After the film thickness of the test piece for measurement was measured, it was allowed to stand still for about 30 minutes under the environment of the measurement temperature (0°C). After confirming that the temperature of the test piece reached the measurement temperature (0° C.), a tensile strength test was performed using a TENSILON universal material testing machine (RTA100, manufactured by ORIENTEC). A tensile strength test was performed under the following conditions.
・Temperature: 0±2°C (within constant temperature and humidity chamber)
・Distance between chucks: 20 mm
- Tensile speed: 300mm/min.
5-1. Flexibility Evaluation of elongation at break When the elongation at break of the test piece at 0°C was 400% or more, it was rated A; when it was 300% or more and less than 400%, B; Evaluation results are shown in Tables 2 to 6.
5-2. Flexibility Evaluation of elastic modulus When the elastic modulus of the test piece at 0°C was 50 MPa or less, it was rated A; Evaluation results are shown in Tables 2 to 6.

6) Evaluation of flexibility (20°C)
A test piece for measurement was prepared in the same process as in "5) Evaluation of flexibility (0°C)". After measuring the film thickness of the test piece for measurement, it was allowed to stand in an environment of measurement temperature (20° C.) for about 30 minutes. After confirming that the temperature of the test piece reached the measurement temperature (20° C.), a tensile strength test was performed using a TENSILON universal material testing machine (RTA100, manufactured by ORIENTEC). A tensile strength test was performed under the following conditions.
・Temperature: 20±2°C (within constant temperature and humidity chamber)
・Distance between chucks: 20mm
- Tensile speed: 300mm/min.
6-1. Flexibility Evaluation of elongation at break When the elongation at break of the test piece at a temperature of 20°C was 400% or more, it was rated A; when it was 300% or more and less than 400%, it was rated B;
6-2. Flexibility Evaluation of elastic modulus If the elastic modulus of the test piece at 20°C was 50 MPa or less, it was rated A, if it was more than 50 MPa and 60 MPa or less, it was rated B, and if it was more than 60 MPa, it was rated C. Evaluation results are shown in Tables 2 to 6.

7) Measurement of adhesive strength 7-1. Adhesion strength (20°C: low temperature)
Using a spacer of 200 μm, the produced curable resin composition was pressure-formed under conditions of 10 MPa and 30 seconds in an environment of 140° C. to obtain a film-formed sample. The obtained film sample was cut into a width of 25 mm and a length of 50 mm. The cut sample was placed together with a 100 μm spacer between the adherend 1 and the adherend 2 described below, and pressurized at 1 MPa for 10 seconds in an environment of 140° C. to prepare an adhesive sample. . The prepared adhesive sample was cured in hot water at 60° C. for 7 days, and then aged in an environment of 23° C. and 50% RH for 1 day to obtain a sample for measurement. The measurement sample was peeled off at 20° C. at a peel rate of 300 mm/min. The 180° peel adhesive strength was measured under the conditions of , and taken as the adhesive strength (20°C).
A result with an adhesive strength (20° C.) of 3.0 N/25 mm or more was rated as "A", and a result with an adhesive strength of less than 3.0 N/25 mm was rated as "B". Evaluation results are shown in Tables 2 to 6. "SA-302 desktop test press" manufactured by Tester Sangyo Co., Ltd. was used for the preparation of film samples and adhesive samples.
Adherend 1: PP plate (thickness: 2 mm)
Adherend 2: CPP film (thickness: 80 μm)
7-2. Adhesion strength (80°C: high temperature)
First, a sample for measurement was obtained by the same process as the above "adhesive strength (20° C.)". Next, the measurement sample was subjected to peeling speed of 300 mm/min. at 80°C. The 180° peel adhesive strength was measured under the conditions of , and was taken as the adhesive strength (80°C).
A result with an adhesive strength (80° C.) of 3.0 N/25 mm or more was rated as "A", and a result with an adhesive strength of less than 3.0 N/25 mm was rated as "B". Evaluation results are shown in Tables 2 to 6. For the preparation of film samples and adhesion samples, "SA-302 desktop test press" manufactured by Tester Sangyo Co., Ltd., a PP plate (thickness: 2 mm) as the adherend 1, and a CPP film as the adherend 2 (thickness: 80 μm) were used.

8) Measurement of heat resistant creep properties (100°C)
Using a spacer of 200 μm, the produced curable resin composition was pressure-formed under conditions of 10 MPa and 30 seconds in an environment of 140° C. to obtain a film-formed sample. The resulting film sample was cut into a width of 25 mm and a length of 25 mm. The cut sample was placed together with a 100 μm spacer between adherends 1 and 2 described below, and pressed under conditions of 1 MPa for 10 seconds in an environment of 140° C. to prepare an adhesive sample (FIG. 1). The prepared adhesive sample was cured in hot water at 60° C. for 7 days, and then aged in an environment of 23° C. and 50% RH for 1 day to obtain a sample for measurement. A weight was placed so that a load of 100 g was applied vertically to the end of the adhesive surface of the obtained measurement sample (Fig. 2), and the heat creep resistance (100 ° C) was measured after 24 hours in a 100 ° C environment. did. Specifically, after 24 hours in an environment of 100° C., the peeled length on the adhesive surface of the measurement sample was less than 10 mm, which was rated as "A", and when it was 10 mm or more, it was rated as "B". Evaluation results are shown in Tables 2 to 6. "SA-302 desktop test press" manufactured by Tester Sangyo Co., Ltd. was used for the preparation of film samples and adhesive samples.
Adherend 1: PP plate (thickness: 2 mm)
Adherend 2: CPP film (thickness: 80 μm)

9) Measurement of heat resistant creep properties (110°C)
First, a sample for measurement was obtained by the same process as in "(9) Thermal creep resistance (100°C)" above. Next, a weight was placed so that a load of 100 g was applied perpendicularly to the edge of the adhesive surface of the obtained measurement sample, and the heat creep resistance (110° C.) was measured after 24 hours in a 110° C. environment. Specifically, after 24 hours in an environment of 110° C., the case where the peel length on the adhesive surface of the measurement sample was less than 10 mm was rated as "A", and the case where it was 10 mm or more was rated as "B". Evaluation results are shown in Tables 2 to 6. In addition, for the preparation of the film formation sample and the adhesion sample, "SA-302 desktop test press" manufactured by Tester Sangyo Co., Ltd. was used as the adherend 1, and a PP plate (thickness: 2 mm) was used as the adherend 2. , CPP films (thickness: 80 μm) were used, respectively.

10) Measurement of heat resistant creep properties (120°C)
First, a sample for measurement was obtained by the same process as in "(9) Thermal creep resistance (100°C)" above. Next, a weight was placed so that a 100 g load was applied perpendicularly to the edge of the adhesive surface of the obtained measurement sample, and the heat creep resistance (120°C) was measured after 24 hours in a 120°C environment. Specifically, after 24 hours in an environment of 120° C., the peel length on the adhesive surface of the measurement sample was less than 10 mm, which was rated as "A", and when it was 10 mm or more, it was rated as "B". Evaluation results are shown in Tables 2 to 6. In addition, for the preparation of the film formation sample and the adhesion sample, "SA-302 desktop test press" manufactured by Tester Sangyo Co., Ltd. was used as the adherend 1, and a PP plate (thickness: 2 mm) was used as the adherend 2. , CPP films (thickness: 80 μm) were used, respectively.

Polyolefins a-1 to a-4, b-1 to b-4
In Examples and Comparative Examples, polyolefins a-1 to a-4 and b-1 to b-4 shown in Table 1 below were used.

Example 1 (Production of curable resin composition X-1)
Polyolefin-based polymer a-1 and polyolefin-based polymer b-1 are mixed so that the modified polyolefin A-1:polyolefin B-1 in the curable resin composition is 70:30 (mass ratio), and the polyolefin-based 1.5 parts by mass of KBM-503 (3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Polymer Co., Ltd.) per 100 parts by mass of the polymer, and 1.5 parts by mass of Perbutyl I ( Using t-Butyl peroxy isopropyl monocarbonate, manufactured by NOF Corporation), a twin-screw extruder (KZW15TW-45/60 MG-NH (-2200) manufactured by Technobell Co., Ltd. (screw outer diameter Φ15 mm, L / D = 45) ) were simultaneously introduced into the supply port of ) and reacted to obtain modified polyolefin A-1 and polyolefin B-1. The operating conditions of the twin-screw extruder were set so that the barrel temperature was 160° C. and the extrusion rate was 1.0-1.5 kg/h. In addition, unreacted additives and by-products were partly removed by placing the end portion of the twin-screw extruder under a reduced pressure environment.
The resulting modified polyolefin A-1 and polyolefin B-1 were cooled and solidified by natural cooling. The mass ratio of the organic polymer C-1 to the total amount of the modified polyolefin A-1 and polyolefin B-1 after cooling and solidification [modified polyolefin A-1 + polyolefin B-1]: organic polymer C-1 = 90:10, and Neostan U-100 (dibutyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.) as a moisture curing catalyst was added in an amount of 0.00 per 100 parts by mass of modified polyolefin A-1 and polyolefin B-1 in total. 005 parts by mass, and mixed using a universal stirrer in an environment of 180° C. to produce a curable resin composition X-1.

Examples 2 to 13, Comparative Examples 1 to 7 (production of curable resin compositions X-2 to X-20)
Same as Example 1 (manufacture of curable resin composition X-1) except that polyolefin polymer a, polyolefin polymer b, and organic polymer C were set to the types and blending amounts shown in Tables 2 and 3. Curable resin compositions X-2 to X-20 were prepared by the method.

Example 14 (Production of curable resin composition X-21)
Polyolefin polymer a-1, Polyolefin polymer a-1; 1.5 parts by mass of KBM-503 (3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Polymer Co., Ltd.) per 100 parts by mass, Polyolefin polymer Coalescence a-1: 100 parts by mass of Perbutyl I (t-Butyl peroxy isopropyl monocarbonate, manufactured by NOF Corporation) of 1.5 parts by mass was used, and a twin-screw extruder (KZW15TW-45/60 MG manufactured by Technobell Co., Ltd.) was used. -NH (-2200) (screw outer diameter Φ15 mm, L/D = 45)) was simultaneously introduced into the supply port and reacted to obtain modified polyolefin A-8. The operating conditions of the twin-screw extruder were set so that the barrel temperature was 160° C. and the extrusion rate was 1.0-1.5 kg/h. In addition, unreacted additives and by-products were partly removed by placing the end portion of the twin-screw extruder under a reduced pressure environment.
The resulting modified polyolefin A-8 was cooled and solidified by natural cooling. Polyolefin B-8 (polyolefin polymer b-1) was added to modified polyolefin A-1 after cooling and solidification so that the mass ratio of modified polyolefin A-8: polyolefin B-8 was 70:30. and the organic polymer C-1 was added so that the mass ratio of [modified polyolefin A-8 + polyolefin B-8]: organic polymer C-1 = 90:10, and Neostan U-100 ( Dibutyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.) is added to 0.005 parts by mass with respect to 100 parts by mass of modified polyolefin A-1, and mixed using a universal stirrer in an environment of 180 ° C. , to produce a curable resin composition X-21.

Example 15 (Production of curable resin composition X-22)
The polyolefin polymer a-1 and the organic polymer C-1 are mixed so that the modified polyolefin A-10 in the curable resin composition: organic polymer C-6 = 86:14 (mass ratio), and the above 1.5 parts by mass of KBM-503 (3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Polymer Co., Ltd.) per 100 parts by mass of the mixture, and 1.5 parts by mass of Perbutyl I (t-Butyl peroxy isopropyl monocarbonate , NOF Co., Ltd.), using a twin-screw extruder (Technobell Co., Ltd. KZW15TW-45/60 MG-NH (-2200) (screw outer diameter Φ15 mm, L / D = 45))) at the same time By adding and reacting, modified polyolefin A-10 and organic polymer C-6 were obtained. The operating conditions of the twin-screw extruder were set so that the barrel temperature was 160° C. and the extrusion rate was 1.0-1.5 kg/h. In addition, unreacted additives and by-products were partly removed by placing the end portion of the twin-screw extruder under a reduced pressure environment.
The resulting modified polyolefin A-10 and organic polymer C-6 were cooled and solidified by natural cooling. Modified polyolefin A-10 in the curable resin composition: polyolefin in the mass ratio of polyolefin B-8 (polyolefin polymer b-1) to modified polyolefin A-10 and organic polymer C-6 after cooling and solidification B-8 = 70:30, [modified polyolefin A-10 + polyolefin B-8]: organic polymer C-6 was added so that C-6 = 90:10, and Neostan U-100 (dibutyltin dilaurate) was added as a moisture curing catalyst. , manufactured by Nitto Kasei Co., Ltd.) was added so as to be 0.005 parts by mass with respect to a total of 100 parts by mass of modified polyolefin A-10 and organic polymer C-6, and a universal stirrer was used in an environment of 180 ° C. A curable resin composition X-22 was produced by mixing.

Example 16 (Production of curable resin composition X-23)
Polyolefin polymer a-1 and polyolefin polymer b-1 were prepared in a curable resin composition so that the ratio of modified polyolefin A-11: polyolefin B-9 was 70:30 (mass ratio), and an organic polymer was added. Combined C-1 was prepared and mixed in a curable resin composition so that [modified polyolefin A-11+polyolefin B-9]:organic polymer C-7=90:10. 1.5 parts by mass of KBM-503 (3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Polymer Co., Ltd.) per 100 parts by mass of the mixture, and 1.5 parts by mass of Perbutyl I (t- Butyl peroxy isopropyl monocarbonate, manufactured by NOF Corporation) to the feed port of the twin-screw extruder (KZW15TW-45/60 MG-NH (-2200) manufactured by Technobell Co., Ltd. (screw outer diameter Φ15 mm, L / D = 45)) They were added at the same time and reacted to obtain a modified mixture of modified polyolefin A-11, polyolefin B-9 and organic polymer C-7. The operating conditions of the twin-screw extruder were set so that the barrel temperature was 160° C. and the extrusion rate was 1.0-1.5 kg/h. In addition, unreacted additives and by-products were partly removed by placing the end portion of the twin-screw extruder under a reduced pressure environment.
The resulting modified mixture was cooled and solidified by natural cooling. Neostan U-100 (dibutyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.) is added as a moisture curing catalyst to the modified mixture after cooling and solidification in an amount of 0.005 part by weight per 100 parts by weight of the total modified mixture. Then, a curable resin composition X-23 was produced by mixing using a universal stirrer in an environment of 180°C.

Organic polymers C-1 to C-5 are as follows.
(C-1): "Trilene (registered trademark) 65" manufactured by Lion Elastomer (DCPD copolymerized olefin, Tg -49°C, weight average molecular weight 50000)
(C-2): "Oppanol (registered trademark) B12SFN" manufactured by BASF (polyisobutylene, Tg -64 ° C., weight average molecular weight 70000)
(C-3): "Oppanol (registered trademark) B15SFN" manufactured by BASF (polyisobutylene, Tg -64 ° C., weight average molecular weight 108000)
(C-4): BASF Corp. "Oppanol (registered trademark) N50SF" (polyisobutylene, Tg -64 ° C., weight average molecular weight 565000)
(C-5): "Aerafin (registered trademark) 180" manufactured by Eastman Chemical Co. (polyolefin, Tg -38 ° C., weight average molecular weight 100000)

Tables 2 to 6 show the preparation conditions of curable resin compositions X-1 to X-23 as Examples 1 to 16 and Comparative Examples 1 to 7 and the results of the various measurements and evaluations. The curable resin compositions shown in Tables 2 to 6 each contain a moisture curing catalyst.

As is clear from Examples 1 to 16 and Comparative Examples 1 to 7, the curable resin composition of the present invention has not only excellent handling properties, adhesive strength under room temperature and high temperature environments after the curing reaction, and heat resistant creep properties, but also It has also been found to be excellent in flexibility, which has a trade-off relationship with heat resistant creep properties.

The curable resin composition of the present invention is excellent in handleability, flexibility, adhesive strength under room temperature and high temperature environments after the curing reaction, and heat resistant creep properties, so it can be suitably used as a hot melt adhesive.

1 adherend 1
2 curable resin composition 3 adherend 2
4 Weight

Claims

containing modified polyolefin A, polyolefin B and organic polymer C,
The modified polyolefin A is a polymer obtained by graft-polymerizing a compound having a moisture-curable functional group to the polyolefin polymer a,
The softening point of the polyolefin polymer a is 80° C. or more and less than 120° C.,
The softening point of the polyolefin B is 120° C. or higher and 170° C. or lower,
The glass transition point of the organic polymer C is −35° C. or lower,
The curable resin composition, wherein the organic polymer C is incompatible with the modified polyolefin A and the polyolefin B.
2. The curable resin composition according to claim 1, wherein the polyolefin B is a polymer obtained by graft-polymerizing a compound having a moisture-curable functional group to the polyolefin polymer b.
2. The curable resin composition according to claim 1, wherein said organic polymer C has a moisture-curable functional group.
2. The curable resin composition according to claim 1, wherein the mass ratio of said modified polyolefin A and said polyolefin B is 90:10 to 60:40.
2. The curable resin composition according to claim 1, wherein the mass ratio of the total amount of the modified polyolefin A and the polyolefin B to the organic polymer C is 95:5 to 75:25.
A hot melt adhesive comprising the curable resin composition according to any one of claims 1 to 5.