JP5648972B2 - Resin composition for encapsulant - Google Patents

Description

The present invention relates to a polyolefin-based resin composition for an encapsulant that has excellent adhesion to a wide range of members such as glass and metal, and is excellent in transparency and weather resistance.

Polyolefin resins such as polyethylene are inexpensive, have excellent processability, and have excellent physical properties such as transparency, weather resistance, heat resistance, and chemical resistance, and are expected to be used as sealing materials for optical applications. ing.
However, since the polyolefin resin has a non-polar molecular structure and is crystalline, there is a drawback in that the adhesiveness with various members is insufficient by themselves. Therefore, it is conceivable to add various tackifying resins and improve the adhesion. However, colored tackifier resins cannot be used for optical applications. Although it can be used as long as it is a colorless and transparent tackifying resin, the tackifying resin has a problem that it is colored or deteriorated when exposed to high temperatures or exposed to ultraviolet rays for a long time.

An object of the present invention is to provide a transparent resin composition for a sealing material having excellent adhesion and excellent workability, heat resistance, and light resistance when performing processing such as melting and processing. To do.

The present inventor has made various studies on the resin composition for a sealing material, and by adding a hydride of a specific C9 aromatic hydrocarbon resin to a polyolefin resin, it has excellent adhesion to various substrates, and The inventors have found that a composition having high transparency and excellent in light resistance and heat resistance can be obtained, and have conceived that the above problems can be solved, and have reached the present invention.

That is, the present invention, (A) seen containing a hydride of a polyolefin resin and (B) hydrogenation of at least 80% of the C9 aromatic hydrocarbon resins, wherein (B) is vinyltoluene 50 wt% or more, A transparent resin composition for a sealing material , wherein a polymer of a C9 polymerizable monomer containing indene in a proportion of 20% by weight or less is hydrogenated .

The encapsulant resin composition of the present invention is transparent, and has excellent processability when performing processing such as melting and processing, while maintaining high transparency and excellent light resistance and heat resistance, and extremely high. It has stability.

The resin composition for a sealing material of the present invention includes (A) a polyolefin resin (hereinafter also referred to as component (A)) and (B) a hydride of a C9 aromatic hydrocarbon resin having a hydrogenation rate of 80% or more. It is obtained by subjecting a composition containing (hereinafter also referred to as component (B)) to a treatment such as melting and processing.

The component (A) is not particularly limited as long as it is an olefin resin,
Examples thereof include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyoctene and the like. These olefin resins may be one kind or a mixture of two or more kinds. Further, for example, a polyolefin obtained by copolymerizing a monomer having two or more types of carbon-carbon double bonds such as mixing a small amount of octene with ethylene may be used. The component (A) is at least one selected from various olefin resins.

The component (B) is obtained by hydrogenating a polymer of a C9-based polymerizable monomer, and has a hydrogenation rate of 80% or more. As the component (B), any of those conventionally used in this field can be used.

The C9 polymerizable monomer is a C9 fraction having a boiling point at atmospheric pressure of about 140 to 280 ° C. among cracked oil fractions obtained by cracking naphtha, specifically, styrene, α- Main examples include methylstyrene, β-methylstyrene, vinyltoluene, indene, alkylindene, dicyclopentadiene, ethylbenzene, trimethylbenzene, and naphthalene. Usually, the C9 polymerizable monomer in the C9 fraction contains about 40% by weight of vinyltoluene and indene, and the remaining about 20% by weight is made of styrene or the like. In the present invention, by distilling the C9 fraction, the indene and high boiling point compounds of the C9 fraction are removed, and the vinyl toluene content in the polymer of the C9 polymerizable monomer is 50% by weight or more. It is preferable to use those prepared so that the indene content is 20% by weight or less (vinyl toluene content / indene content = 2.5 or more). The vinyltoluene content in the polymer of the C9 polymerizable monomer is more preferably 55% by weight or more, and further preferably 60% by weight or more, and the higher the better. The indene content is more preferably 15% by weight or less, and even more preferably 10% by weight or less, and the lower the better.

The polymer of the C9 polymerizable monomer is obtained by polymerizing a C9 polymerizable monomer by cationic polymerization by a known method. As such a polymer of the C9 polymerizable monomer, a known product can be used. Usually, the softening point (measured by the ring and ball method according to JIS K2207) is about 70 to 150 ° C., preferably 80 to 150 ° C., and the weight average molecular weight (polystyrene conversion value by gel permeation chromatography) is 300 to 2000. About, preferably about 500-1500 is used.

The polymerization of the C9 polymerizable monomer is preferably performed using a non-phenolic Friedel-Crafts type catalyst. The non-phenolic Friedel-Crafts type catalyst refers to a catalyst in which phenols are not substantially detected from a C9 aromatic hydrocarbon resin obtained by polymerization using a catalyst. As a detection method, for example, a coloration method using iron (III) chloride (Eiichi Funakubo, “Organic Compound Confirmation Method I”, Yokendo, (1967), Chapter 1, pages 9-12 ) Etc. Examples of the phenols to be used include those having an —OH group in the molecule such as phenol or cresol, xylenol, p-tert-butylphenol, p-octylphenol, nonylphenol, and other alkyl-substituted phenols. can give.

Examples of the non-phenolic Friedel-Crafts catalyst include boron trifluoride gas or boron trifluoride ether complex. When such a catalyst is used, there is a tendency that coloring is difficult even when a hydride of a C9 aromatic hydrocarbon resin is heated. Therefore, in the polymerization of the C9 aromatic hydrocarbon resin in the present invention, it is preferable not to use a Friedel-Crafts type catalyst containing phenols such as a boron trifluoride phenol complex.

The hydrogenation rate of the said (B) component needs to be 80% or more. In particular, the component (B) having a hydrogenation rate of 90% or more has a very high compatibility with the olefin resin, so that it becomes possible to obtain a resin composition for a sealing material having extremely high transparency. Moreover, the one where the hydrogenation rate of the said (B) component is higher is preferable from the viewpoint of the light resistance of the resin composition for sealing materials obtained.

Hydrogenation rate, determined by NMR measurement method, ¹ H- spectrum of aromatic rings appearing near 7ppm of ¹ H-NMR of the C9 aromatic hydrocarbon resins and the resulting C9 aromatic hydrocarbon resins hydride It calculates based on the following formula (1) from the area.
Hydrogenation rate = {1- (spectral area of hydride of C9 aromatic hydrocarbon resin / spectral area of unhydrogenated C9 aromatic hydrocarbon resin)} × 100 (%) (1)

The hydrogenation reaction is performed by appropriately adjusting the conditions in the presence of a hydrogenation catalyst so that the hydrogenation rate of the C9 petroleum resin becomes a target level.

In the hydrogenation, a polymer of a C9 polymerizable monomer is usually reacted in the presence of a hydrogenation catalyst. The hydrogenation pressure and reaction temperature may be appropriately determined depending on the catalyst used, but are usually about 0.98 to 29.4 MPa, preferably about 1.0 to 24.5 MPa, about 150 to 400 ° C., preferably Is about 200-350 degreeC. When the hydrogenation pressure is less than 0.98 MPa or when the reaction temperature is less than 150 ° C., the hydrogenation reaction hardly proceeds. On the other hand, when the hydrogenation pressure exceeds 29.4 MPa, it is not preferable from the viewpoint of economy and safety, and when the reaction temperature exceeds 400 ° C., the hydrogenolysis reaction of the resin becomes remarkable. This is also not preferable. However, if a catalyst capable of causing a reaction at a hydrogenation pressure of 0.98 MPa or less is used, the described pressure conditions are not limited. As the reaction format, a batch system, a flow system (fixed bed system, fluidized bed system, etc.), etc. can be employed.

Known hydrogenation catalysts can be used. Specifically, various kinds of metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium, molybdenum, osmium, iridium, rhenium, copper, iron, or metal compounds such as oxides or sulfides thereof can be used. . These hydrogenation catalysts may be used alone or in combination. Further, such a hydrogenation catalyst may be used by being supported on various known carriers having a large surface area such as alumina, silica (diatomaceous earth), activated carbon, titania, silica alumina and the like. The supported amount is 0.0001 g to 1 g, preferably 0.005 g to 0.7 g, per 1 g of the carrier. Among these catalysts, nickel / diatomaceous earth catalysts are preferable from the viewpoint of hydrogenation efficiency of aromatic rings and cost. In this case, the supported amount of nickel is preferably 20 to 150% by weight. In the present invention, the supported amount X% means an amount of nickel X parts by weight supported on 100 parts by weight of the carrier. A known catalyst may be used as the catalyst, or it may be prepared independently by combining known catalyst preparation methods. Examples of the form of the catalyst include granular, powdery, bowl-like, cylindrical, and extrusion molds, but are not particularly limited.

In the case of the batch type, the amount of the catalyst used is usually about 0.01 to 10% by weight, preferably about 0.1 to 3.0% by weight, relative to the component (B) or the decompressed product described below. is there. If it is less than 0.01% by weight, the hydrogenation reaction hardly proceeds, and if it exceeds 10% by weight, it is not economical. Moreover, the reaction time of hydrogenation is about 1 to 7 hours normally, Preferably it is about 2 to 7 hours.

The hydrogenation reaction is performed in a molten state of a polymer of a C9 polymerizable monomer or in a state dissolved in a solvent. As the solvent, any solvent that is inert to the reaction and easily melts the raw materials and products is sufficient, and specifically, hydrocarbons are exemplified. Examples of the hydrocarbons include cyclohexane, n-hexane, n-heptane, decalin and the like, preferably cyclohexane.

The said solvent may be used individually by 1 type, and may be used in combination of 2 or more type. An appropriate amount of the solvent used is preferably an amount such that the solid content is in the range of 10 to 80% by weight with respect to the component (B) or the decompressed product described below, but is not particularly limited. .

After the hydrogenation, the solvent, catalyst and the like are removed by a conventional method such as distillation under reduced pressure or filtration.

Although the said vacuum distillation is not specifically limited, Usually, a pressure reduction process is performed in the range for about 10 hours or less on the conditions of about 6.7 KPa or less and about 200 degreeC or more. By setting the decompression treatment conditions to 6.7 KPa or less and 200 ° C. or more, low boiling components can be sufficiently removed. Preferably, the decompression treatment condition is 5.2 KPa or less, more preferably 2.6 KPa or less under a temperature condition of about 210 to 280 ° C.

The softening point of the component (B) is preferably about 70 to 150 ° C. In this case, it is possible to obtain a resin composition for a sealing material that is excellent in processability and excellent in adhesiveness, transparency, and durability when performing treatment such as melting and processing. When it is less than 70 ° C., it is insufficient in terms of heat resistance of the obtained sheet, and when it exceeds 150 ° C., there is a problem in that the viscosity at the time of melting is high and the workability is deteriorated. More preferably, it is 90-140 degreeC.

The weight average molecular weight of the component (B) is preferably about 800 to 3000. In this case, it is possible to obtain a resin composition for a sealing material that is excellent in processability and excellent in adhesiveness, transparency, and durability when performing treatment such as melting and processing. If the weight average molecular weight is less than 800, there is a problem in terms of the heat resistance of the resulting sheet, and if it exceeds 3000, the viscosity at the time of melting is high, and the workability deteriorates. More preferably, it is 900-2500.

The blending amount of the component (B) is 1 to 200 parts by weight, preferably 1 to 50 parts by weight with respect to 100 parts by weight of the component (A).

The resin composition for an encapsulant of the present invention uses an excellent feature such as transparency, light resistance, and heat resistance to make electronic materials such as liquid crystal, organic EL, plasma display, solar cell modules, etc. into glass. It can be used for the purpose of sealing between metal and metal.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “parts” means “parts by weight” unless otherwise specified.

Example 1
As a hydride of 80 parts of ethylene-octene copolymer (trade name Engage 8200, manufactured by Dow Chemical Co., Ltd.) and C9 aromatic hydrocarbon resin , resin a (produced by Arakawa Chemical Industries, Ltd. , hydrogenation rate: 94% 20 parts were heated and melted at about 200 ° C. and mixed. This molten mixture was dropped and pressure-bonded onto a glass plate and an aluminum plate substrate of about 50 mm × 20 mm × 1 mm, and then cooled to room temperature and solidified. The excess part which protruded from the base material was removed with the cutter, and the sheet | seat of about 50 mm x 20 mm x 1 mm was produced.

Example 2 and Comparative Example 1
A sheet was prepared in the same manner as in Example 1 except that the hydride of the C9 aromatic hydrocarbon resin used was changed as shown in Table 1.

Comparative Example 2
Ethylene-octene copolymer (trade name Engage 8200, manufactured by Dow Chemical Co., Ltd.) 80 parts and hydride of C9 aromatic hydrocarbon resin (trade name “Arcon M100”, manufactured by Arakawa Chemical Industries, Ltd., hydrogenation rate 20 parts of 70%, vinyltoluene / indene ratio = 1.1) were heated and melted at about 200 ° C. and mixed. The molten mixture was pressed on a glass plate and an aluminum plate substrate of about 50 mm × 20 mm × 1 mm, and then cooled to room temperature and solidified. The excess part which protruded from the base material was removed with the cutter, and the sheet | seat of about 50 mm x 20 mm x 1 mm was produced.

Comparative Example 3
100 parts of an ethylene-octene copolymer (trade name Engage 8200, manufactured by Dow Chemical Co., Ltd.) was heated and melted at about 200 ° C. The molten mixture was pressed on a glass plate and an aluminum plate substrate of about 50 mm × 20 mm × 1 mm, and then cooled to room temperature and solidified. The excess part which protruded from the base material was removed with the cutter, and the sheet | seat of about 50 mm x 20 mm x 1 mm was produced.

(Evaluation of adhesion)
The surface adhesion of the sheet having a thickness of about 1 mm that was press-bonded and produced on a glass plate and aluminum was evaluated. The results are shown in Table 1. In Table 1, "◎" in the item of "Adhesion" indicates that the sheet is completely adhered to the substrate and cannot be easily peeled off with a finger, and "X" indicates that the sheet is easily removed from the substrate with a finger. Indicates peeling off.

(Evaluation of transparency)
The transparency of the sheet in the present invention was visually determined. Judgment criteria are as follows. The results are shown in Table 1.
○: Transparent △: Slightly cloudy but transparent ×: Slightly cloudy

(Evaluation of heat resistance)
As for the heat resistance of the sheet in the present invention, the colorability when heated at 180 ° C. for 4 hours was visually determined. Judgment criteria are as follows. The results are shown in Table 1.
○ No coloring. Δ Slightly colored. X Coloring is remarkable.

(Evaluation of light resistance)
The light resistance of the sheet in the present invention was placed in a light resistance tester (xenon lamp irradiation, manufactured by HERAEUS, SUNTEST light resistance tester) and irradiated with light for 72 hours. Thereafter, the degree of coloring of the test piece was visually determined. Judgment criteria are as follows. ○ No coloring. Δ Slightly colored. X Coloring is remarkable. The results are shown in Table 1.

The terms in Table 1 mean the following:
Polyolefin: ethylene-octene copolymer (trade name Engage 8200, manufactured by Dow Chemical Co., Ltd.)
MASAKI fat a: vinyltoluene 58%, a polymerizable C9 fractions containing 9% indene, boron trifluoride gas cationic polymerized C9 aromatic hydrocarbon resins hydride as catalyst (Arakawa Chemical Industries Co. (Production hydrogenation rate = 94%)
Resin b: hydride of C9 aromatic hydrocarbon resin obtained by cationic polymerization of a polymerizable C9 fraction containing 58% vinyltoluene and 9% indene using boron trifluoride gas as a catalyst (manufactured by Arakawa Chemical Industries, Ltd.) (Hydrogenation rate = 99%)
P100: hydride of C9 aromatic hydrocarbon resin (trade name “Arcon P100” manufactured by Arakawa Chemical Industries, Ltd.) Hydrogenation rate = 90% Vinyltoluene / indene ratio = 1.1)
M100: hydride of C9 aromatic hydrocarbon resin (trade name “ Arcon M100 ” manufactured by Arakawa Chemical Industries, Ltd. = 70% hydrogenation rate)

Claims (5)

(A) seen containing a hydride of a polyolefin resin and (B) hydrogenation of at least 80% of the C9 aromatic hydrocarbon resins, wherein (B) is vinyltoluene 50 wt% or more, indene 20 wt% or less A transparent resin composition for an encapsulant, which is obtained by hydrogenating a polymer of a C9 polymerizable monomer contained in a ratio of The transparent resin composition for a sealing material according to claim 1, wherein the softening point of the hydride of the (B) C9 aromatic hydrocarbon resin is 70 to 150 ° C. The transparent resin composition for encapsulating materials according to claim 1 or 2, wherein the weight average molecular weight of the hydride of (B) C9 aromatic hydrocarbon resin is 800 to 3000. The transparent product according to any one of claims 1 to 3, wherein the hydride of the (B) C9 aromatic hydrocarbon resin is obtained by hydrogenating a polymer obtained by using a non-phenolic Friedel-Crafts catalyst. Resin composition for sealing material. The transparent sealing according to any one of claims 1 to 4 , wherein a hydride of (B) a C9 aromatic hydrocarbon resin is 1 to 50 parts by weight with respect to 100 parts by weight of the (A) polyolefin resin. Resin composition for materials.