JP2008163121A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in a water-resistance and further excellent in an adhesion property and an anti-blocking property. <P>SOLUTION: The resin composition contains (A) 10-90 mass% of a specific maleic anhydride-modified polypropylene-based resin, and (B) 10-90 mass% of a specific maleic anhydride-modified hydrogenated styrene-based thermoplastic elastomer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition, and more particularly, to a resin composition having excellent water resistance and further excellent adhesion and blocking resistance.

  Adhesives containing a resin composition are used in various fields, and various required performances are required depending on the purpose. For example, the materials of the adherends include glass, iron, copper, aluminum, polyolefin resin, polyethylene terephthalate resin, ethylene-vinyl acetate copolymer resin, etc., metal foil, sheet, film, and composite sheets and films thereof. Good adhesion is also required between different materials. Further, depending on the use conditions such as outdoor use and moisture contact, water resistance needs to be improved. Furthermore, in recent years, in consideration of the environment, it has been desired to add a non-halogen resin composition that does not generate harmful gases during incineration.

  In order to satisfy these required performances, various resin compositions have been developed in the past. For example, Patent Document 1 describes a composite of an olefin polymer composition and a metal, and a specific elastomer is used as an adhesive. This adhesive is said to have good adhesion even in a combination of different materials such as an olefin polymer composition and a metal, but in general, an adherend bonded with these elastomeric adhesives is kept in water for a long time. When immersed, peeling starts from a portion that comes into contact with water, and a decrease in adhesive force is promoted, so the use is limited.

  Patent Document 2 describes a coating agent in which a polar monomer graft crosslinked resin containing a polar monomer and a crosslinking agent in a propylene elastomer and a styrene elastomer is dissolved in an organic solvent. Although this coating agent is said to be excellent in adhesive performance, because of the elastomer structure in which the basic structure of both elastomers has a segment of a repeating unit that is partially crystalline, the above-described decrease in adhesive strength in water is caused. There were problems such as possibility and difficulty in producing water-based emulsion products due to insufficient addition amount of polar groups.

  Patent Document 3 describes a non-chlorine modified polyolefin composition, which has excellent adhesion to non-polar sheets such as polypropylene, polyethylene, and ethylene-propylene copolymer, and is weather resistant. It is said that it is excellent also in physical properties, such as property. However, since the above composition is a simultaneous modification of maleic acid and styrene monomer in a limited range within a limited range, the reaction system is complicated, and the adhesive strength may be lowered depending on the blending ratio and reaction conditions.

  Patent Document 4 describes an aqueous resin composition containing a polyolefin resin composition modified with an unsaturated carboxylic acid or an anhydride thereof. In the aqueous resin composition, it is described that blocking is reduced by blending modified starch within a limited range. However, since this composition is obtained by blending substances having completely different molecular weights and chemical structures, water resistance and adhesive strength may be lowered depending on the modification conditions and blending.

  Patent Document 5 describes a polyolefin-based composition in which a specific polyolefin resin and a specific thermoplastic elastomer are combined. This composition is a polyolefin resin composition having excellent weather resistance, molding processability, heat resistance, wear resistance, and deformation recovery. However, the adhesive resin composition has a weak adhesive force, and further improvement is required.

JP 2002-283518 A JP 2006-37000 A JP 2001-139642 A JP 2004-285227 A JP 2005-248110 A

  The present invention has been made under such circumstances, and an object of the present invention is to provide a resin composition having excellent water resistance and excellent adhesion and blocking resistance.

As a result of intensive studies to achieve the above object, the present inventors have found that the above problem can be solved by combining a specific amorphous polypropylene resin and a specific styrene thermoplastic elastomer.
That is, the present invention was obtained by modifying (A) an amorphous polypropylene resin having a weight average molecular weight of 70,000 to 200,000 and a molecular weight distribution (Mw / Mn) of 5 or less with maleic anhydride. Maleic anhydride-modified polypropylene resin having a maleic acid modification rate of 0.3 to 10.0% and a weight average molecular weight of 40,000 to 150,000, and (B) a weight average molecular weight of 5, 000 to 200,000, a hydrogenated styrene-based thermoplastic elastomer having a styrene content of 20 to 40% by mass, obtained by modifying with maleic anhydride, a maleic acid modification rate of 0.3 to 10.0%, The present invention provides a resin composition containing 10 to 90% by mass of a maleic anhydride-modified hydrogenated styrene thermoplastic elastomer having a weight average molecular weight of 5,000 to 200,000.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which is excellent in water resistance, and also excellent in adhesiveness and blocking resistance is provided, and this resin composition is the resin composition for adhesion, the primer of a coating material / ink, or the resin composition for binders Are preferably used. In particular, the resin composition of the present invention has both adhesiveness and blocking resistance, both of which have been difficult in the past. As a result of this characteristic, the resin composition can be used under various conditions (materials, uses, etc.), and the material to be coated can be easily handled in the step of applying the resin composition and the subsequent processing steps.

  The resin composition of the present invention comprises (A) an amorphous polypropylene resin modified with maleic anhydride and (B) a hydrogenated styrene thermoplastic elastomer modified with maleic anhydride.

  The component (A) of the present invention can be obtained by modifying an amorphous polypropylene resin with maleic anhydride, and the amorphous polypropylene resin can be obtained by copolymerizing propylene and other monomers. Examples of the monomer include ethylene, an α-olefin having 4 to 20 carbon atoms, a cyclic olefin, a vinyl aromatic compound, and a polyene compound.

  Examples of the α-olefin having 4 to 20 carbon atoms include chain olefins such as linear olefins and branched olefins, and examples of linear olefins include 1-butene, 1-pentene, and 1-hexene. Examples of branched olefins include 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, and the like.

  Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, cyclopentene, 3-methylcyclopentene, cyclohexene, 3-methylcyclohexene Etc. are exemplified.

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinyl xylene, and the like.

  Examples of the polyene compound include conjugated polyene compounds and non-conjugated polyene compounds. Examples of the conjugated polyene compound include aliphatic conjugated polyene compounds such as linear aliphatic conjugated polyene compounds and branched aliphatic conjugated polyene compounds, and alicyclic conjugated polyene compounds. Examples of the non-conjugated polyene compound include an aliphatic non-conjugated polyene compound, an alicyclic non-conjugated polyene compound, and an aromatic non-conjugated polyene compound. These conjugated polyene compounds or conjugated polyene compounds may have an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, or the like.

  Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene and the like. Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclopentadiene, and the like. The Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, and the like. Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexene, 5-vinyl-2-norbornene, and 5-ethylidene-2-norbornene. Examples of the aromatic non-conjugated polyene compound include divinylbenzene and vinylisopropenylbenzene.

  The weight average molecular weight of the amorphous polypropylene resin is 70,000 to 200,000, preferably 70,000 to 150,000. If the weight average molecular weight is in the above range, maleic anhydride modification treatment is easy and a highly adhesive resin can be obtained. The molecular weight distribution (Mw / Mn) is 5 or less, preferably 4 or less, more preferably 3 or less. Blocking resistance improves because molecular weight distribution is 5 or less. The molecular weight distribution is a numerical value calculated from a weight average molecular weight (Mw) and a number average molecular weight (Mn) measured by gel permeation chromatography (GPC).

The intrinsic viscosity [η] of the amorphous polypropylene resin is preferably 0.7 to 10 dl / g. If it is the said range, coexistence of the adhesiveness of a resin composition and blocking resistance will be attained. From the above viewpoint, it is preferably 0.9 to 8 dl / g, and more preferably 1.2 to 7 dl / g.
The intrinsic viscosity [η] is measured using an Ubbelohde viscometer in 135 ° C. tetralin.

  The polypropylene-based resin of the present invention is an amorphous polypropylene-based resin that does not have an elastomer structure with a segment of a repeating unit that is partially crystalline. By using the amorphous polypropylene resin, water resistance is improved along with the adhesiveness of the resin composition.

Differential scanning calorimetry (DSC) can be used as an amorphous standard. In the temperature range of −100 to 200 ° C., a crystal melting peak with a crystal melting heat of 1 J / g or more and a crystallization heat of 1 J / g or more. It is preferred that none of the crystallization peaks are observed. The heat of crystal fusion and the heat of crystallization can be measured under the following conditions.
(I) About 5 mg of a sample is heated from room temperature to 200 ° C. at a temperature rising rate of 30 ° C./min, and then kept at 200 ° C. for 5 minutes.
(Ii) The temperature is decreased from 200 ° C. to −100 ° C. at a temperature decreasing rate of 10 ° C./min, and then kept at −100 ° C. for 5 minutes.
(Iii) The temperature is increased from −100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min.
The peaks observed in the above (ii) and (iii) are a crystallization peak and a crystal melting peak, respectively. In the present invention, it is preferable that there is no peak of 1 J / g or more.

  In the present invention, it is preferable to use an amorphous polypropylene resin produced with a metallocene catalyst. By using an amorphous polypropylene resin synthesized with a metallocene catalyst, the blocking resistance of the resin composition is improved. Examples of the metallocene catalyst include, for example, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35008. JP, JP 61-130314, JP 3-163088, JP 4-268307, JP 9-12790, JP 9-87313, JP 11-80233. And metallocene catalysts described in JP-A-10-508055 and the like.

  In the present invention, a conventionally known technique can be used as a method of modifying an amorphous polypropylene resin with maleic anhydride, and the method is not particularly limited. For example, after melting an amorphous polypropylene resin, a method of adding an organic peroxide and maleic anhydride, or after dissolving an amorphous polypropylene resin in a solvent such as toluene or xylene, And a method of adding maleic anhydride. A twin-screw extruder used for acid modification and dynamic crosslinking of polyolefin elastomers can also be used, but from the viewpoint of increasing the addition reaction rate of maleic anhydride, special stirring that controls the reaction temperature with a heat medium It is preferable to use a reaction kettle with wings.

  The (A) component of the present invention has a weight average molecular weight of 40,000 to 150,000, preferably 70,000 to 120,000. If it is less than 40,000, the adhesion performance may be lowered, and if it exceeds 150,000, handling becomes difficult due to high viscosity. The maleation rate is 0.3 to 10% by mass, preferably 1 to 4% by mass. When the amount is less than 0.3% by mass, it is difficult to lower the adhesive performance and to form an aqueous emulsion. When the amount exceeds 10% by mass, the viscosity is high and handling is difficult. In the present invention, the maleation rate means the ratio of maleic anhydride to the component (A) and / or the component (B). The melt viscosity is preferably 25,000 to 45,000 mPa · s at 185 ° C., more preferably 27,000 to 33,000 mPa · s. If it is less than 25,000 mPa · s, the adhesion performance may be lowered, and if it exceeds 45,000 mPa · s, handling becomes difficult. The acid value is preferably 5 to 20 mgKOH / g, more preferably 8 to 15 mgKOH / g. If it is less than 5 mgKOH / g, it is difficult to make an aqueous emulsion, and if it exceeds 20 mgKOH / g, it becomes difficult to handle due to high viscosity.

  The component (B) of the present invention can be obtained by modifying a hydrogenated styrene thermoplastic elastomer with maleic anhydride. The hydrogenated styrenic thermoplastic elastomer is obtained by hydrogenating a block copolymer comprising at least one polymer block mainly composed of styrene and at least one polymer block mainly composed of a conjugated diene compound. It is a hydrogenated block copolymer, Comprising: The styrene content which occupies in a hydrogenated block copolymer is 20-40 mass%.

  The hydrogenated styrene thermoplastic elastomer is, for example, a block copolymer of polybutadiene and polystyrene, a block copolymer of polyisoprene and polystyrene, or a block of polybutadiene or ethylene-butadiene random copolymer and polystyrene. The copolymer can be obtained by hydrogenation, and in particular, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, or styrene-butadiene / isoprene-styrene block copolymer is hydrogenated. A hydrogenated block copolymer obtained as described above is preferred.

  The hydrogenated styrenic thermoplastic elastomer has a weight average molecular weight of 5,000 to 200,000, preferably 40,000 to 120,000. When the weight average molecular weight is in the above range, a highly adhesive resin excellent in blocking resistance can be obtained. Moreover, the melt flow rate (MFR) measured by 230 degreeC and the load 21.18N according to JISK-7210 is 1-200 g / 10min, More preferably, it is 2-100g / 10min, More preferably, it is 3-80g / 10 minutes. By being in this range, the modification performance with maleic anhydride is easy, and the adhesion performance is improved.

  In the present invention, a conventionally known technique can be used as a method for modifying a hydrogenated styrene-based thermoplastic elastomer with maleic anhydride, and the method is not particularly limited. For example, the method exemplified in the maleic anhydride modification treatment of the amorphous polypropylene resin can be used.

  The (B) hydrogenated styrene-based thermoplastic elastomer-modified maleic anhydride of the present invention is a block copolymer having a styrene content of 20 to 40% by mass and a water having a weight average molecular weight of 5,000 to 200,000. It is a maleated product of an additive and has a maleation ratio of 0.3 to 10% by mass, preferably 1 to 4% by mass. When the maleation rate is less than 0.3% by mass, it is difficult to lower the adhesive performance and to make an aqueous emulsion, and when it exceeds 10% by mass, it is difficult to handle due to high viscosity. Further, the melt viscosity is 5,000 to 40,000 mPa · s at 210 ° C., preferably 15,000 to 30,000 mPa · s. If it is less than 5,000 mPa · s, the adhesion performance may be lowered, and if it exceeds 40,000 mPa · s, handling becomes difficult. Furthermore, an acid value is 5-20 mgKOH / g, Preferably it is 8-15 mgKOH / g. If it is less than 5 mgKOH / g, it is difficult to make an aqueous emulsion, and if it exceeds 20 mgKOH / g, it becomes difficult to handle due to high viscosity.

  In this invention, the resin composition excellent in blocking resistance, adhesiveness, and water resistance is obtained by using the said (A) component and (B) component together. The blending ratio (mass ratio) of component (A): component (B) is 1: 9 to 9: 1, preferably 3: 7 to 7: 3, more preferably 5.5: 4.5 to 4.5. : 5.5. When the component (A) is less than 1: 9, the water resistance and adhesion performance deteriorate, and when it exceeds 9: 1, the blocking resistance decreases.

  The resin composition of the present invention can be obtained by mixing the component (A) and the component (B) as described above. After mixing the amorphous polypropylene resin and the hydrogenated styrene thermoplastic elastomer, You may modify | denaturate with maleic anhydride.

  In the resin composition of the present invention, in addition to the components (A) and (B), (C) hydrogenated petroleum resin can be further added. By adding the component (C), the compatibility of the component (A) and the component (B) is improved, thereby achieving long-term storage of the adhesive and stable long-term adhesion.

As the component (C), C ₅ fraction naphtha cracked oil, a hydrogenation product of C ₆ -C ₁₁ fraction, other olefinic fractions homopolymers and copolymers, aliphatic petroleum resins And alicyclic petroleum resins and aliphatic-alicyclic copolymer resins. Examples of the C ₅ fraction include isoprene; cyclopentadiene; 1,3-pentadiene; methylbutenes such as 2-methyl-1-butene and 2-methyl-2-butene; such as 1-pentene and 2-pentene. Pentenes; and dicyclopentadiene are preferred. As C ₆ -C ₁₁ fraction above, indene; styrene; o-, m-, p-vinyl toluene; methyl indene;; alpha-, methylstyrene such as β- methyl styrene ethyl indene, vinyl xylene; and, Propenylbenzene is preferred. As the other olefinic fractions, butene, hexene, heptene, octene, butadiene and octadiene are preferable.

  As the component (C), a resin containing an alicyclic component is preferable. By containing an alicyclic component, the compatibility of the component (A) and the component (B) is improved. Moreover, the thing whose softening point of (C) component is 130-150 degreeC is used preferably. When the softening point is within the above range, the compatibility is improved and the storage stability is further increased.

  The content of the component (C) is preferably 1 to 10 parts by mass, more preferably 3 to 8 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). When the amount is less than 1 part by mass, the effect of adding the component (C) cannot be obtained, and when the amount exceeds 10 parts by mass, the adhesive performance is lowered.

  (C) A commercial item can also be used for (C) component, For example, "Arcon P-140" (made by Arakawa Chemical Industry Co., Ltd.) and "Clearon P-150" (made by Yasuhara Chemical Co., Ltd.) are mentioned.

  In the resin composition of the present invention, a resin composition in which the component (A) and the component (B) are partially crosslinked using the (D) crosslinking agent can be used. Adhesiveness is further improved by the partial crosslinking treatment, and long-term storage and long-term stable adhesion of the adhesive are achieved by improving compatibility.

  The component (D) of the present invention is a compound containing a reactive substituent at the terminal of glycerin or polyglycerin, and examples of the reactive substituent include a group having a double bond at the terminal and an epoxy group. Preferable examples include compounds represented by general formula (I), (II) or (III). Moreover, radical polymerization initiators, such as an organic peroxide and organic perester, can also be used in combination with the crosslinking agent of (D).

  In general formula (I)-(III), n shows the integer of 1-3.

  The component (D) of the present invention is preferably a compound represented by the general formula (I) or (III), more preferably a compound of the general formula (I) or (III) in which n is 3. .

  The content of the component (D) is preferably 0.5 to 5 parts by mass, more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is. If the amount is less than 0.5 parts by mass, the effect of improving the compatibility cannot be obtained. If the amount exceeds 5 parts by mass, a partial crosslinking reaction does not occur and an unreacted product remains.

  The adhesive resin composition of the present invention can be dissolved in a solvent and used as a solvent-based adhesive. Preferred solvents include aromatic hydrocarbon solvents such as toluene, xylene and high boiling point solvents, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate and acetic acid. Examples thereof include ester solvents such as butyl.

  In addition, the adhesive resin composition of the present invention can be used as an aqueous emulsion adhesive. An aqueous emulsion can be prepared by adding an emulsifier, alcohol and water. The solid concentration is preferably 20 to 40% by mass, more preferably 25 to 35% by mass.

  The resin composition of the present invention has excellent adhesiveness to various materials, and can be used as an adhesive resin composition, a paint / ink primer, or a binder resin composition. As an adhesive resin composition, it can be used for adhesion of sheets, films and molded articles in automobiles, home appliances, electronic materials, foods, medical fields, etc., for example, applied to the synthetic resin side of synthetic resin laminated metal foil, Thermoplastic elastomers such as food packaging such as heat-sealing lid materials with excellent water resistance for sealing glass containers, PTP packaging materials such as pharmaceuticals, foods, and health foods, and automotive window glass. And an adhesive in an ethylene-vinyl acetate copolymer resin or the like used for an adhesive laminate of glass and a protective material for solar cells.

  Examples The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Production Example 1 (Production of maleic anhydride-modified amorphous polypropylene resin composition)
100 parts by weight of “Tough Selenium SCC25” (manufactured by Sumitomo Chemical Co., Ltd.) was sequentially charged into a four-necked flask equipped with a nitrogen supply pipe and a cooler in an oil bath and equipped with a stirring blade and a thermometer. The temperature was raised to 170 ° C. over 3 hours. When the resin temperature in the system reached around 170 ° C., the system was rotated at 250 rpm to keep the system at a uniform temperature of 170 ° C. During this period, the dropping funnel was kept at 60 ° C., and 4 parts by mass of molten maleic anhydride (Nippon Yushi Co., Ltd.) and 1 part by mass of organic peroxide “Parhexa 25B” (Nippon Yushi Co., Ltd.) were added. Hold in each dropping funnel. When the inside of the system was uniform and stable, the maleic anhydride and the organic peroxide were dripped little by little at a mass ratio of 4: 1. Ten minutes after the start of the dropping, the stirring speed was increased to 500 rpm to keep the stirring at a high speed, and a predetermined amount was dropped sequentially, and the reaction was performed at a system temperature of 150 to 170 ° C. for about 2 hours in a nitrogen atmosphere. After completion of the dropwise addition, the finishing reaction was performed at 150 to 160 ° C. for about 1 hour with high-speed stirring. The physical properties of the obtained maleic anhydride-modified amorphous polypropylene resin composition are as follows: maleation ratio is 1.3% (unreacted maleic anhydride is 0.1% or less), and melt viscosity is 27, at 185 ° C. The acid value was 100 mPa · s, the acid value was 12.6 mgKOH / g, and the weight average molecular weight was 81,610 (measured by GPC method).

Production Example 2 (Production of maleic anhydride-modified hydrogenated styrene thermoplastic elastomer)
In a four-necked flask equipped with a nitrogen supply pipe, a cooler, and a pressure reducing device in an oil bath and equipped with a stirring blade and a thermometer, 50 parts by mass of a high boiling point solvent “Ipsol 150” (manufactured by Idemitsu Kosan Co., Ltd.) Then, 100 parts by mass of “Tuftec H1041” (manufactured by Asahi Kasei Chemicals Corporation) was sequentially added, and the temperature was raised to 185 ° C. over 3 hours under a nitrogen stream. When the resin temperature in the system reached around 185 ° C., the system was rotated at 250 rpm to maintain a uniform temperature of 185 ° C. in the system. During this period, the dropping funnel was kept at 60 ° C., and 4 parts by mass of molten maleic anhydride (Nippon Yushi Co., Ltd.) and 1 part by mass of organic peroxide “Parhexa 25B” (Nippon Yushi Co., Ltd.) were added. Hold in each dropping funnel. When the inside of the system was uniform and stable, the maleic anhydride and the organic peroxide were dripped little by little at a mass ratio of 4: 1. Ten minutes after the start of dropping, the stirring speed was increased to 500 rpm to maintain high-speed stirring, and a predetermined amount was dropped sequentially and reacted at a system temperature of 185 to 200 ° C. for about 2 hours in a nitrogen atmosphere. After completion of dropping, the reaction was finished at 185 to 200 ° C. for about 1 hour with high-speed stirring. Thereafter, the vacuum pump was operated for about 1 hour to reduce the pressure in the reaction system, and the residual high boiling point solvent was distilled out of the system. The physical properties of the obtained maleic anhydride-modified hydrogenated styrene thermoplastic elastomer are as follows: maleation ratio is 1.2% (unreacted maleic anhydride is 0.1% or less), and melt viscosity is 27,500 mPa at 210 ° C. -S, the acid value was 9.8 mgKOH / g, and the weight average molecular weight was 76,500 (measured by GPC method).

Production Example 3 (Production of maleic anhydride-modified polypropylene resin composition)
Maleic anhydride-modified polypropylene resin composition according to the method described in Production Example 1 except that “VESTPLAST # 750” (polypropylene resin manufactured by Degussa AG: resin manufactured with Ziegler Natta catalyst) was used instead of “Tufselen SCC25” The product was synthesized. As for the physical properties of the resin composition, the maleation ratio was 1.3% (unreacted maleic anhydride was 0.1% or less), the melt viscosity was 23,000 mPa · s at 185 ° C., and the acid value was 29.9 mgKOH / g, The weight average molecular weight was 51,000 (measured by GPC method).

Production Example 4 (Production of Resin Composition by Simultaneous Maleic Anhydride Modification Treatment for Mixture of Amorphous Polypropylene Resin Composition and Hydrogenated Styrenic Thermoplastic Elastomer)
In a four-necked flask equipped with a nitrogen supply pipe, a cooler, and a pressure reducing device in an oil bath and equipped with a stirring blade and a thermometer, 25 parts by mass of a high boiling point solvent “Ipsol 150” (manufactured by Idemitsu Kosan Co., Ltd.) 50 parts by mass of “Tough Selenium SCC25” (manufactured by Sumitomo Chemical Co., Ltd.) and 50 parts by mass of “Tough Tech H1041” (manufactured by Asahi Chemicals Co., Ltd.) are added successively, and the temperature is increased to 185 ° C. over 3 hours under nitrogen flow The temperature rose. When the resin temperature in the system was around 185 ° C., the system was rotated at 250 rpm to maintain a uniform temperature of 185 ° C. in the system. During this period, the dropping funnel was kept at 60 ° C., and 4 parts by mass of molten maleic anhydride (Nippon Yushi Co., Ltd.) and 1 part by mass of organic peroxide “Parhexa 25B” (Nippon Yushi Co., Ltd.) were added. Hold in each dropping funnel. When the system was uniform and stable, maleic anhydride and organic peroxide were added dropwise in a mass ratio of 4: 1. Ten minutes after the start of dropping, the stirring speed was increased to 500 rpm to maintain high-speed stirring, and a predetermined amount was dropped sequentially and reacted at a system temperature of 185 to 200 ° C. for about 2 hours in a nitrogen atmosphere. Thereafter, the vacuum pump was operated for about 1 hour to reduce the pressure in the reaction system, and the residual high-boiling solvent was distilled out of the system. As for the physical properties of the obtained resin composition, the maleation ratio is 1.2% (unreacted maleic anhydride is 0.1% or less), the melt viscosity is 19,500 mPa · s at 210 ° C., and the acid value is 9. It was 7 mgKOH / g.

Example 1 (Production of adhesive solvent-dissolved product (1))
10 parts by mass of the maleic anhydride-modified amorphous polypropylene resin composition obtained in Production Example 1 and 10 parts by mass of the maleic anhydride-modified hydrogenated styrene thermoplastic elastomer obtained in Production Example 2 were added to the methylcyclohexane solvent. Add to 64 parts by weight, raise the temperature to 100 ° C over 1.5 hours, further dissolve completely over 1 hour, cool to 70 ° C, add 16 parts by weight of ethyl acetate and stir for 30 minutes Thus, an adhesive solvent-dissolved product having a solid content of 20% by mass and a viscosity of 84.3 mPa · s (25 ° C.) was obtained.

Example 2 (Production of adhesive solvent-dissolved product (2))
18 parts by mass of the resin composition obtained in Production Example 4, 2 parts by mass of “Alcon P-140” (manufactured by Arakawa Chemical Co., Ltd.), and 63 parts by mass of methylcyclohexane were mixed and mixed for 100 hours over 1.5 hours. The temperature was raised to 0 ° C., and after complete dissolution over 1 hour, the mixture was cooled to 70 ° C., 16 parts by mass of ethyl acetate was added, and the mixture was stirred for 30 minutes, solid content 20% by mass, viscosity 92.0 mPa · s ( 25 ° C.) was obtained.

Example 3 (Production of adhesive solvent-dissolved product (3))
18 parts by mass of the resin composition obtained in Production Example 4 was collected in a four-necked flask equipped with a cooler in an oil bath and equipped with a stirring blade and a thermometer, and 65 parts by mass of methylcyclohexane was added. The temperature was raised to 100 ° C. at a stirring speed of 120 rpm over 1.5 hours. During this time, the dropping funnel was kept at 50 ° C., and 0.23 parts by mass of “Epolite 80MF” (manufactured by Kyoeisha Chemical Co., Ltd.) was mixed and dissolved in 3.5 parts by mass of MEK (methyl ethyl ketone) solvent. When the reaction temperature became uniform at 97 ° C., the reaction temperature was kept at 90 to 100 ° C., and the solution was successively dropped from the funnel for about 4 hours, and then a final partial crosslinking reaction was performed for 1 hour. Thereafter, the mixture was cooled to 65 ° C. and 15.5 parts by mass of MEK solvent was added to obtain an adhesive / solvent dissolved product having a solid content of 19.8% by mass and a viscosity of 110 mPa · s (25 ° C.).

The following resin compositions were synthesized as comparative examples.
(Comparative Example 1) The solid content was determined by the method described in Example 1 except that “Tuff Selenium SCC25” was used instead of “Maleic anhydride-modified amorphous polypropylene resin composition obtained in Production Example 1”. An adhesive solvent-dissolved product having a mass of 20% by mass and a viscosity of 72.8 mPa · s (25 ° C.) was obtained.
(Comparative Example 2) Solid content 20 according to the method described in Example 1 except that “Tuftec H1041” was used instead of “Maleic anhydride-modified hydrogenated styrene thermoplastic elastomer obtained in Production Example 2”. An adhesive / solvent-dissolved product having a mass% and a viscosity of 69.5 mPa · s (25 ° C.) was obtained.
(Comparative Example 3) “Tough selenium SCC25” instead of “maleic anhydride-modified amorphous polypropylene resin composition obtained in Production Example 1”, “maleic anhydride-modified hydrogenated styrene system obtained in Production Example 2” The adhesive solvent-dissolved product having a solid content of 20% by mass and a viscosity of 76.4 mPa · s (25 ° C.) was obtained by the method described in Example 1 except that “Tuftec H1041” was used instead of “thermoplastic elastomer”. It was.
(Comparative Example 4) The maleic anhydride-modified polypropylene resin composition obtained in Production Example 3 instead of the “maleic anhydride-modified amorphous polypropylene resin composition obtained in Production Example 1” (the polypropylene resin is The adhesive solvent-dissolved product having a solid content of 20% by mass and a viscosity of 78.2 mPa · s (25 ° C.) was obtained by the method described in Example 1 except that a compound synthesized with a Ziegler-Natta catalyst was used.
(Comparative Example 5) Instead of “maleic anhydride-modified amorphous polypropylene resin composition obtained in Production Example 1”, a commercially available polypropylene elastomer maleated product having a partial crystallinity was used, and methylcyclohexane was used. In addition to the use of toluene and methyl ethyl ketone in place of ethyl acetate, an adhesive solvent-soluble product having a solid content of 20% by mass and a viscosity of 83.5 mPa · s (25 ° C.) was obtained by the method described in Example 1. .

Example 4 (Production of aqueous emulsion product)
85 parts by mass of the maleic anhydride-modified amorphous polypropylene resin composition obtained in Production Example 1, 15 parts by mass of the maleic anhydride-modified hydrogenated styrene thermoplastic elastomer obtained in Production Example 2, and 31.5 of methylcyclohexane The mass part was put into a 1 L apparatus equipped with a helical ribbon blade and a cooler, and the resin was melted and dissolved over 4 hours, and the temperature was raised to 97 ° C. at 60 rpm. After 30 minutes, a mixed alcohol solution of 7.5 parts by weight of normal propyl alcohol (NPA) and 50.4 parts by weight of isopropyl alcohol (IPA) was added and stirred for 30 minutes, and the temperature in the system was kept at 85 ° C. Thereafter, 16.0 parts by mass of Esomine S / 25 (manufactured by Lion Akzo Co., Ltd.) and 4.0 parts by mass of deformer 399 (manufactured by Sannobuco Co., Ltd.) were added and stirred for 10 minutes. ) 28.4 parts by mass was added, and the system temperature was raised to 100 ° C. Thereafter, the rotational speed of the stirring blade was gradually increased to 500 rpm, and a small amount of 470 parts by mass of ion-exchanged water was dropped over 8 hours. During this time, a very small amount of a mixture of methylcyclohexane, NPA / IPA alcohol, and water was distilled out of the system by 40 batch operations from the 1L cooling circulation line. After completion of the ion-exchange water injection, the system was stirred for about 30 minutes, the temperature in the system was lowered to 60 ° C., and filtered through 250 mesh to extract the aqueous emulsion. The aqueous emulsion has a solid content concentration of 29.4% by mass, pH 9.9, an average particle diameter of 1 to 1.5 μm, a viscosity of 29.0 mPa · s (25 ° C.), and the residual solvent is NPA 0.17% by mass and IPA 0.48 mass% and methylcyclohexane were 0 mass%.

Comparative Example 6 (Production of aqueous emulsion product (2))
In place of "90 parts by mass of the maleic anhydride-modified amorphous polypropylene resin composition obtained in Production Example 1, 10 parts by mass of the maleic anhydride-modified hydrogenated styrene thermoplastic elastomer obtained in Production Example 2" Except for using 100 parts by mass of the maleic anhydride-modified polypropylene resin composition obtained in Production Example 3, the solid content concentration was 29.8% by mass, pH 9.3, average particle size 1 by the method described in Example 4. An aqueous emulsion having a residual solvent of 0.20% by mass, IPA of 0.50% by mass, and methylcyclohexane of 0% by mass was prepared with a viscosity of ˜1.5 μm, a viscosity of 27.0 mPa · s (25 ° C.).

  The following tests were conducted using the resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 6. The results are shown in Table 1.

(Blocking resistance test)
50 μm polyester film (manufactured by Toray Industries, Inc.) 200 mm × 200 mm on one side is dried with a 20% solid content solvent-soluble product or a 30% solid content aqueous emulsion product obtained in each example and comparative example. It apply | coated so that it might become conversion 5 micrometers, and it was made to dry at 110 degreeC for 15 minutes, and obtained the single-sided adhesive coating film. This film was cut to a width of 15 mm, and then two adhesive coating surfaces were stacked in the same direction, and left at 72 ° C. for 72 hours under a load of 0.1 MPa at 40 ° C. Using this test sample, the blocking resistance was evaluated by two tests, a peel test based on JIS K6854 and a feeling when peeled by hand.
The test based on the above JIS K6854 measured the peel strength (unit: N / 15 mm) at a tensile speed of 5 cm / min, and showed the average value of the obtained values.
The evaluation based on the sensation when peeled off by hand is intended to evaluate the blocking resistance at a level that cannot be determined by the test based on JIS K6854. Specifically, the test sample is fixed on a table and the upper side is evaluated. One end of the film was pulled up by hand at a speed of about 5 cm / min, the degree of resistance to the hand and the ease of peeling at that time were observed, and evaluated according to the following criteria.

Evaluation standard A: There is no sense of resistance to the hand, and it is easy to peel off.
○: There is very little resistance to the hand and it is slightly difficult to peel off.
Δ: There is a sense of resistance to the hand.
X: 1 (N / 15 mm) or more in the test based on JIS K6854

(Adhesion test)
(1) Substrate / Substrate: Aluminum / Glass 40 μm aluminum foil (manufactured by Sumi Light Aluminum Foil Co., Ltd.) 200 mm × 200 mm on one side of the 20% by mass solid content concentration obtained in each Example and Comparative Example The solvent-dissolved product was applied to a dry equivalent of 5 μm and dried at 110 ° C. for 15 minutes to obtain a single-sided adhesive-coated aluminum foil. The aluminum foil was cut to a width of 15 mm, heat-sealed on a glass plate of the same size (hot press (0.3 MPa) at 200 ° C. for 3 seconds), and then subjected to a tensile test according to JIS K6854. Tensile test conditions were 25 ° C. at a speed of 100 mm / min, 90-degree peeling (test piece 15 mm width), and evaluated according to the following criteria.
A: 8.0 or more ○: 6.5 or more to less than 8.0 Δ: 4.5 or more to less than 6.5 x: less than 4.5 (unit: N / 15 mm)

(2) Substrate / Substrate: Aluminum / PP
40 μm aluminum foil (manufactured by Sumikara Aluminum Foil Co., Ltd.) 200 mm × 200 mm on one side, the 20 mass% solid solution concentration solvent-soluble product obtained in each Example and Comparative Example was applied to a dry equivalent of 5 μm. And dried at 110 ° C. for 15 minutes to obtain a single-sided adhesive-coated aluminum foil. This aluminum foil is cut to a width of 15 mm, and then heat-sealed (hot press (0.1 MPa) at 180 ° C. for 1 second) on a 300 μm PP film (made by Idemitsu Kosan Co., Ltd.) of the same size, and then subjected to a tensile test according to JIS K6854. went. The tensile test was performed at 25 ° C. with a speed of 100 mm / min and 180-degree peeling (test piece width of 15 mm), and evaluated based on the above (1).

(3) Substrate / Substrate: PET / PP
50 μm polyester film (manufactured by Toray Industries, Inc.) 200 mm × 200 mm on one side was coated with the solvent-dissolved product having a solid content concentration of 20% by mass obtained in each Example and Comparative Example so as to have a dry conversion of 4 μm, and 110 ° C. And dried for 15 minutes to obtain a single-sided adhesive-coated polyester film. This film is cut to a width of 15 mm, and then heat-sealed (hot press (0.3 MPa) at 110 ° C. for 3 seconds) on a PP film of the same size (manufactured by Idemitsu Kosan Co., Ltd.), and a tensile test is performed according to JIS K6854. It was. The tensile test was performed at 25 ° C. with a speed of 100 mm / min and 180-degree peeling (test piece width of 15 mm), and evaluated based on the above (1).

(4) Substrate / Substrate: PP / PP
50 μm polypropylene film (manufactured by Idemitsu Kosan Co., Ltd.) 200 mm × 200 mm on one side, the 30% solid content aqueous emulsion product obtained in Example 4 and Comparative Example 6 was applied to a dry conversion of 5 μm, It was made to dry at 110 degreeC for 15 minutes, and the single-sided adhesive coating polypropylene film was obtained. After cutting this film to a width of 15 mm, heat-seal [hot press (0.3 MPa) at 110 ° C. for 3 seconds] on a polypropylene film of the same size (manufactured by Idemitsu Kosan Co., Ltd.) and perform a tensile test according to JIS K6854. It was. The tensile test was performed at 25 ° C. with a speed of 100 mm / min and 180-degree peeling (test piece width of 15 mm), and evaluated based on the above (1).

(Water resistance test)
40 μm aluminum foil (manufactured by Sumi Light Aluminum Foil Co., Ltd.) 200 mm × 200 mm on one side, the solvent-dissolved product having a solid content concentration of 20% by mass obtained in Examples 1 to 3 and Comparative Examples 1 to 5 was converted to 5 μm in dry conversion. This was applied and dried at 110 ° C. for 15 minutes to obtain a single-sided adhesive-coated aluminum foil. The aluminum foil was cut to a width of 15 mm, and then heat-sealed (hot pressed at 200 ° C. for 2 seconds (0.3 MPa)) on a glass plate of the same size. The test piece was immersed in deionized water according to JIS K6829 (treatment time: 0, 100 hours), and then a tensile test was performed. The tensile test was performed at 25 ° C. at a rate of 100 mm / min and 90-degree peeling (test specimen 15 mm width), and the peel strength reduction rate was calculated by the following formula.
In addition, about the water-emulsion goods (Example 4 and Comparative Example 6), the same immersion process was performed using the test sample obtained by the method as described in the above-mentioned adhesion test (4).
(Peel strength reduction rate)
= {Strength (0 hour) -strength (after 100 hours)} / strength (0 hour) × 100
The water resistance was evaluated according to the following criteria.
A: Peel strength reduction rate less than 10% B: 10% to less than 20% Δ: 20% to less than 40% x: 40% or more

(Storage stability test)
The storage stability at 25 ° C. of the solvent-soluble product having a solid content concentration of 20% by mass and the aqueous emulsion product having a solid content concentration of 30% by mass obtained in each Example and Comparative Example were evaluated. The state from immediately after production to 6 months was observed, and the period until the phase separation tendency was observed was examined.
◎: Very good ○: Good △: Somewhat bad ×: Bad

As shown in Example 1, the resin composition containing a maleic anhydride modified product of an amorphous polypropylene resin composition and a maleic anhydride modified product of a hydrogenated styrene thermoplastic elastomer obtained in the present invention is Excellent blocking resistance and water resistance, and good adhesion performance. In addition, as shown in Examples 2 and 3, the above performance and the like can be further improved by partial cross-linking and blending of additives. Further, as shown in Example 4, the resin composition of the present invention is also excellent as an aqueous emulsion adhesive.
On the other hand, as shown in Comparative Examples 1 to 3, the above-mentioned required performance is not satisfied unless the amorphous polypropylene resin and / or the hydrogenated thermoplastic elastomer is modified with maleic anhydride.
In the present invention, it is important to use a specific amorphous polypropylene resin. In Comparative Example 4 using a polypropylene resin synthesized with a Ziegler-Natta catalyst, good blocking resistance and adhesion cannot be obtained. In Comparative Example 5 using an elastomer having a segment of a repeating unit having a part of crystallinity, the water resistance is extremely poor.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which is excellent in water resistance, and also excellent in adhesiveness and blocking resistance is provided, and this resin composition is the resin composition for adhesion, the primer of a coating material / ink, or the resin composition for binders Are preferably used.

Claims (7)

(A) Maleic acid modification rate obtained by modifying an amorphous polypropylene resin having a weight average molecular weight of 70,000 to 200,000 and a molecular weight distribution (Mw / Mn) of 5 or less with maleic anhydride 10 to 90% by mass of maleic anhydride-modified polypropylene resin having a weight average molecular weight of 40,000 to 150,000, and (B) a weight average molecular weight of 5,000 to 200, 000, a hydrogenated styrene thermoplastic elastomer having a styrene content of 20 to 40% by mass, obtained by modification with maleic anhydride, a maleic acid modification rate of 0.3 to 10.0% by mass, and a weight average molecular weight A resin composition containing 10 to 90% by mass of a maleic anhydride-modified hydrogenated styrene thermoplastic elastomer having a molecular weight of 5,000 to 200,000.   The resin composition according to claim 1, wherein the amorphous polypropylene resin is a resin synthesized with a metallocene catalyst.   The resin composition according to claim 1 or 2, obtained by subjecting a mixture of an amorphous polypropylene resin and a hydrogenated styrene thermoplastic elastomer to a maleic anhydride modification treatment.   The resin composition according to any one of claims 1 to 3, comprising 1 to 10 parts by mass of (C) a hydrogenated petroleum resin with respect to 100 parts by mass of the total amount of the component (A) and the component (B). The resin composition according to any one of claims 1 to 4, wherein (D) the general formula (I), (II) or (III)

(In the formula, n represents an integer of 1 to 3.)
The resin composition obtained by processing with the crosslinking agent represented by these.   The solvent type adhesive agent containing the resin composition in any one of Claims 1-5.   The water-system emulsion adhesive containing the resin composition in any one of Claims 1-5.