WO2011115140A1 - 樹脂成形品用補強シート、樹脂成形品の補強構造および補強方法 - Google Patents
樹脂成形品用補強シート、樹脂成形品の補強構造および補強方法 Download PDFInfo
- Publication number
- WO2011115140A1 WO2011115140A1 PCT/JP2011/056116 JP2011056116W WO2011115140A1 WO 2011115140 A1 WO2011115140 A1 WO 2011115140A1 JP 2011056116 W JP2011056116 W JP 2011056116W WO 2011115140 A1 WO2011115140 A1 WO 2011115140A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin molded
- molded product
- reinforcing
- heating
- reinforcing sheet
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
- B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/266—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate
Definitions
- the present invention relates to a resin molded article reinforcing sheet, a resin molded article reinforcing structure and a reinforcing method, and more particularly to a resin molded article reinforcing sheet, a resin molded article reinforcing structure using the same, and a resin molded article reinforcing method.
- the rib is usually molded integrally with the resin plate, and at the time of molding, there is a sink on the surface of the resin plate at the portion reinforced with the rib, so that the appearance of the resin plate is impaired. is there.
- the reinforcing layer of the steel sheet reinforcing sheet needs to be heated to 160 to 200 ° C. to be cured. Therefore, when such a steel plate reinforcing sheet is attached to a resin plate and heated to 160 to 200 ° C., there is a problem that the resin plate deteriorates or melts.
- a reinforcing sheet including a steel sheet reinforcing sheet may be left for a long time in a high-temperature atmosphere (a temperature at which the resin sheet does not melt) after being stuck to a resin plate or a steel plate. It is desired to effectively prevent a decrease in force.
- the object of the present invention is to be able to easily reinforce a resin molded product while preventing deterioration or melting of the resin molded product by heating at a relatively low temperature without impairing the aesthetic appearance.
- An object of the present invention is to provide a reinforcing sheet for a resin molded product, a reinforcing structure for a resin molded product, and a reinforcing method, which can effectively prevent a decrease in reinforcing force after a long time has passed.
- the reinforcing sheet for resin molded product of the present invention is a reinforcing sheet for resin molded product comprising a constraining layer and a reinforcing layer laminated on the constraining layer, and the reinforcing sheet for resin molded product has a thickness of 2.0 mm.
- the bending strength of 1 mm displacement after sticking to a polypropylene plate and heating at 80 ° C. for 10 minutes is 3N or more, the maximum bending strength is 30N or more, and the following high-temperature adhesive retention rate R is 80% or more. It is characterized by.
- Hot adhesive holding ratio R (1 hour after heating the adhesive force A 1h after heating 100 ° C. of 1000 hours adhesion A 1000h / 100 °C) ⁇ 100 Adhesive strength A 1000h after heating at 100 ° C. for 1000 hours: The reinforcing layer is adhered to a polypropylene plate, heated at 80 ° C. for 10 minutes, and then heated at 100 ° C. for 1000 hours, and then peeled at 300 mm / min in accordance with JIS Z0237 ( 2000) Adhesive strength to polypropylene plate measured by 90 degree peel test Adhesive strength A 1h after heating at 100 ° C. for 1 hour: The reinforcing layer is adhered to the polypropylene plate, heated at 80 ° C.
- the reinforcing layer Is attached to a polypropylene plate, heated at 80 ° C. for 10 minutes, and then peeled at a speed of 300 mm / min according to JIS Z02. It is preferable that the adhesive strength A 10 m with respect to the polypropylene plate measured by a 90 degree peel test of 37 (2000) is 15 N / 25 mm or more.
- the adhesive strength A 1h after heating at 100 ° C. for 1 hour is 50 N / 25 mm or more.
- the reinforcing layer has a storage elastic modulus at 25 ° C. of 500 kPa or more and a storage elastic modulus at 80 ° C. of 500 kPa or less.
- the adhesive force A 0 at room temperature with respect to a polypropylene plate measured by a 90-degree peel test of JIS Z0237 (2000) at a peeling speed of 300 mm / min is 0.3 N / 25 mm. It is suitable that it is above.
- the reinforcing layer is formed from a heat-bonding pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition contains conjugated dienes. It is preferable that a hydrogenated product of a monomer polymer is contained, and that the pressure-sensitive adhesive composition further contains a tackifier, and It is preferable to contain a cyclic saturated hydrocarbon resin, and it is preferable to further contain a terpene resin, and the mixing ratio of the tackifier is the hydrogenated product. The amount is preferably 40 to 200 parts by weight with respect to 100 parts by weight.
- the reinforcing structure of the resin molded product of the present invention is a resin molded product reinforcing sheet comprising a constraining layer and a reinforcing layer laminated on the constraining layer, and is then bonded to the resin molded product at 80 ° C. or higher.
- the resin molded product is reinforced by heating and causing the resin molded product reinforcing sheet to adhere to the resin molded product, and the resin molded product reinforcing sheet is attached to a 2.0 mm thick polypropylene plate.
- the bending strength of 1 mm displacement after heating at 80 ° C. for 10 minutes is 3N or more, the maximum bending strength is 30N or more, and the following high-temperature adhesion retention R is 80% or more.
- Hot adhesive holding ratio R (1 hour after heating the adhesive force A 1h after heating 100 ° C. of 1000 hours adhesion A 1000h / 100 °C) ⁇ 100 Adhesive strength A 1000h after heating at 100 ° C. for 1000 hours: The reinforcing layer is adhered to a polypropylene plate, heated at 80 ° C. for 10 minutes, and then heated at 100 ° C. for 1000 hours, and then peeled at 300 mm / min in accordance with JIS Z0237 ( 2000) Adhesive strength to polypropylene plate measured by 90 degree peel test Adhesive strength A 1h after heating at 100 ° C. for 1 hour: The reinforcing layer is adhered to the polypropylene plate, heated at 80 ° C.
- the product reinforcing sheet is preheated to 80 ° C. or higher, and then the resin molded product reinforcing sheet is molded into the resin molded product. It is preferable to adhere to.
- the method for reinforcing a resin molded product of the present invention includes a step of attaching a reinforcing sheet for a resin molded product comprising a constraining layer and a reinforcing layer laminated on the constraining layer to the resin molded product, and the resin molding A step of reinforcing the resin molded product by heating the product reinforcing sheet and / or the resin molded product to 80 ° C. or more and bringing the resin molded product reinforcing sheet into close contact with the resin molded product, A reinforcing sheet for resin molded product is attached to a polypropylene plate having a thickness of 2.0 mm, the bending strength of 1 mm displacement after heating at 80 ° C. for 10 minutes is 3 N or more, the maximum bending strength is 30 N or more, and the following high temperature
- the adhesive retention rate R is 80% or more.
- Hot adhesive holding ratio R (1 hour after heating the adhesive force A 1h after heating 100 ° C. of 1000 hours adhesion A 1000h / 100 °C) ⁇ 100 Adhesive strength A 1000h after heating at 100 ° C. for 1000 hours: The reinforcing layer is adhered to a polypropylene plate, heated at 80 ° C. for 10 minutes, and then heated at 100 ° C. for 1000 hours, and then peeled at 300 mm / min in accordance with JIS Z0237 ( 2000) Adhesive strength to polypropylene plate measured by 90 degree peel test Adhesive strength A 1h after heating at 100 ° C. for 1 hour: The reinforcing layer is adhered to the polypropylene plate, heated at 80 ° C.
- the adhesion strength to a polypropylene plate measured by a 90-degree peel test of JIS Z0237 (2000) at a peeling rate of 300 mm / min.
- the resin molded product reinforcing sheet is preliminarily placed at 80 ° C. Heated to above, then it is preferable to adhere the reinforcing sheet for resin molded product to the resin molded article.
- the reinforcing layer of the reinforcing sheet for the resin molded product is adhered to the resin molded product,
- the constraining layer and the resin molded product can be firmly adhered to each other by the reinforcing layer, and the rigidity of the reinforcing sheet for resin molded products can be obtained.
- Can be improved. Therefore, the resin molded product can be reliably reinforced by the reinforcing sheet for resin molded product.
- the resin molded product can be reinforced with a simple structure including a constraining layer and a reinforcing layer while achieving a reduction in thickness and weight.
- the reinforcing layer has a high temperature adhesive retention rate R within a specific range, so that the constraining layer and the resin molded product are brought into close contact with each other by heating at a relatively low temperature as described above. Then, even if it passes for a long time in a high temperature atmosphere, the adhesiveness of a constrained layer and a resin molded product can be maintained favorable, or the adhesiveness can be improved.
- FIG. 2 shows the relationship between the heating time at 100 ° C. and the adhesive strength in Examples 1 to 3 and Comparative Example 1.
- the reinforcing sheet for resin molded product of the present invention includes a constraining layer and a reinforcing layer laminated on the constraining layer.
- the constraining layer is provided for imparting toughness to the reinforcing layer after sticking and heating, and is preferably formed of a sheet-like material that is lightweight and thin, and can be closely integrated with the reinforcing layer, Specific examples include glass cloth, resin-impregnated glass cloth, nonwoven fabric, metal foil, carbon fiber, and polyester film.
- the glass cloth is a cloth made of glass fiber, and includes a known glass cloth.
- the resin-impregnated glass cloth is obtained by impregnating the above glass cloth with a synthetic resin such as a thermosetting resin or a thermoplastic resin, and may be a known one.
- a thermosetting resin an epoxy resin, a urethane resin, a melamine resin, a phenol resin etc. are mentioned, for example.
- the thermoplastic resin include vinyl acetate resin, ethylene-vinyl acetate copolymer (EVA), vinyl chloride resin, EVA-vinyl chloride resin copolymer, and the like.
- EVA ethylene-vinyl acetate copolymer
- the above-mentioned thermosetting resin and thermoplastic resin can be used alone or in combination, respectively.
- Nonwoven fabrics include, for example, wood fibers (wood pulp, etc.), cellulosic fibers (eg, regenerated cellulosic fibers such as rayon, semi-synthetic cellulosic fibers such as acetate, natural cellulosic fibers such as hemp and cotton, For example, those blended yarns), polyester fibers, polyvinyl alcohol (PVA) fibers, polyamide fibers, polyolefin fibers, polyurethane fibers, cellulosic fibers (hemp, or hemp and other cellulosic fibers) and the like.
- Nonwoven fabric may be mentioned.
- Examples of the metal foil include known metal foils such as aluminum foil and steel foil.
- Carbon fiber is a fiber made of carbon as a main component, and includes known ones.
- polyester film examples include a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, and a polybutylene terephthalate (PBT) film.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- PET film is used.
- a resin-impregnated glass cloth is preferably used in consideration of adhesion, strength and cost.
- the thickness of the constraining layer is, for example, 0.05 to 2.0 mm, preferably 0.1 to 1.0 mm.
- the reinforcing layer is formed by molding the pressure-sensitive adhesive composition into a sheet shape.
- the pressure-sensitive adhesive composition is a heat-bonding type, and specifically exhibits adhesiveness (tackiness), for example, by heating at 80 ° C. or higher.
- the pressure-sensitive adhesive composition contains, as a main component, for example, a hydrogenated product (hydride) of a monomer polymer containing conjugated dienes.
- the monomer preferably contains a conjugated diene as an essential component, and a copolymerizable monomer copolymerizable with the conjugated diene as an optional component.
- conjugated dienes examples include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), chloroprene (2-chloro-1,3-butadiene), and the like.
- the copolymerizable monomer is a monomer having at least one double bond, and examples thereof include aliphatic vinyl monomers (olefins) such as ethylene, propylene, and isobutylene (2-methylpropene), Examples thereof include aromatic vinyl monomers such as styrene, and cyano group-containing vinyl monomers such as (meth) acrylonitrile.
- aliphatic vinyl monomers such as ethylene, propylene, and isobutylene (2-methylpropene
- aromatic vinyl monomers such as styrene
- cyano group-containing vinyl monomers such as (meth) acrylonitrile.
- copolymerizable monomers can be used alone or in combination of two or more.
- an aromatic vinyl monomer is used.
- the monomer include a block or random copolymer of a conjugated diene and a copolymerizable monomer, and a block copolymer is preferable.
- Specific examples include styrene-butadiene-styrene block copolymers and styrene-isoprene-styrene block copolymers.
- the blending ratio of the copolymerizable monomer is, for example, 5 to 80 parts by weight, preferably 15 to 50 parts by weight with respect to 100 parts by weight of the conjugated diene.
- the blending ratio of the copolymerizable monomer (preferably aromatic vinyl monomer, more preferably styrene) and the conjugated diene (preferably butadiene or isoprene) is, for example, 50% on a weight basis. % By weight or less / 50% by weight or more (weight ratio of copolymerizable monomer and conjugated diene), preferably 40% by weight or less / 60% by weight or more, and usually 10% by weight or more / 90% by weight It is as follows. In other words, the blending ratio of the copolymerizable monomer is, for example, 50% by weight or less, preferably 40% by weight or less, based on the total amount of the conjugated dienes and the copolymerizable monomer. 10% by weight or more.
- the unsaturated bond (double bond portion) derived from the conjugated diene is completely hydrogenated or partially hydrogenated, preferably completely hydrogenated.
- the hydrogenated product include styrene-ethylene-butylene-styrene copolymer (SEBS, more specifically SEBS block copolymer), styrene-ethylene-propylene-styrene copolymer (SEPS, and more). Specific examples thereof include SEPS block copolymers.
- the hydrogenated product does not substantially contain unsaturated bonds due to hydrogenation of the above-described polymer, it is difficult to be thermally deteriorated in a high-temperature atmosphere, so that the heat resistance of the reinforcing layer can be improved.
- the weight average molecular weight (polystyrene equivalent value by GPC) of the hydrogenated product is, for example, 20000 or more, preferably 25000 to 100,000.
- melt flow rate (MFR) of the hydrogenated product is a temperature of 190 ° C. and a weight of 2.16 kg, for example, 10 g / 10 min or less, preferably 5 g / 10 min or less, usually 0.1 g / 10 min or more. It is.
- the melt flow rate (MFR) of the hydrogenated product is, for example, 50 g / 10 min or less, preferably 20 g / 10 min or less at a temperature of 200 ° C. and a weight of 5 kg, and usually 0.1 g / 10 min or less. It is.
- SEBS is preferable.
- the pressure-sensitive adhesive composition preferably further contains a tackifier.
- the tackifier is contained in the pressure-sensitive adhesive composition in order to improve the adhesion between the reinforcing layer and the resin molded product or the constraining layer, or to improve the reinforcing property when reinforcing the resin molded product.
- tackifiers include rosin resins, terpene resins (including terpene phenol copolymers (terpene-modified phenol resins), hydrogenated terpene resins, etc.), coumarone indene resins, alicyclic saturated hydrocarbons.
- Resin petroleum resin (for example, hydrocarbon petroleum resin such as aliphatic / aromatic copolymer petroleum resin, aromatic petroleum resin, etc.), phenol resin, and the like.
- the softening point of the tackifier is, for example, 50 to 150 ° C, preferably 50 to 130 ° C.
- the softening point of the tackifier is measured by the ring and ball method.
- the glass transition point of the tackifier is, for example, 0 to 100 ° C., preferably 20 to 60 ° C.
- the glass transition point is measured by a DSC method or the like.
- the weight average molecular weight of the tackifier is, for example, 100 to 10,000, preferably 200 to 2,000.
- the weight average molecular weight of the tackifier is calculated by a GPC method converted using standard polystyrene (PS) having a known weight average molecular weight.
- PS polystyrene
- ⁇ Tackifiers can be used alone or in combination of two or more.
- terpene resins and alicyclic saturated hydrocarbon resins are preferably used from the viewpoint of compatibility with the hydrogenated product.
- alicyclic saturated hydrocarbon resins are used alone, different types (preferably two types) of alicyclic saturated hydrocarbon resins are used together, alicyclic saturated hydrocarbons.
- an alicyclic ring is preferably used.
- Group saturated hydrocarbon resin and terpene resin are used in combination.
- the blending ratio of the tackifier is, for example, 40 to 200 parts by weight, preferably 50 to 170 parts by weight with respect to 100 parts by weight of the hydrogenated product.
- the blending ratio of the tackifier is less than the above range, the adhesion between the reinforcing layer, the resin molded product and the constraining layer is sufficiently improved, or the reinforcing property at the time of reinforcement of the resin molded product is sufficient. It may not be possible to improve.
- the reinforcing layer may become brittle.
- the ratio of one alicyclic saturated hydrocarbon resin to the other alicyclic saturated hydrocarbon resin is the weight ratio (one Part by weight of the alicyclic saturated hydrocarbon resin / part by weight of the other alicyclic saturated hydrocarbon resin), for example, 10/90 to 50/50, preferably 20/80 to 40/60. is there.
- the ratio of the terpene resin to the alicyclic saturated hydrocarbon resin is a weight ratio (parts by weight of terpene resin /
- the number of parts by weight of the alicyclic saturated hydrocarbon resin is, for example, 1/99 to 80/20, preferably 5/95 to 60/40.
- the pressure-sensitive adhesive composition includes a filler, an anti-aging agent, a softening agent (for example, naphthenic oil, paraffinic oil, etc.), a thixotropic agent (for example, montmorillonite), a lubricant (for example, stearic acid and the like), pigments, scorch inhibitors, stabilizers, antioxidants, ultraviolet absorbers, colorants, fungicides, flame retardants, and the like can be added at an appropriate ratio.
- a softening agent for example, naphthenic oil, paraffinic oil, etc.
- a thixotropic agent for example, montmorillonite
- a lubricant for example, stearic acid and the like
- pigments for example, scorch inhibitors, stabilizers, antioxidants, ultraviolet absorbers, colorants, fungicides, flame retardants, and the like can be added at an appropriate ratio.
- the filler examples include magnesium oxide, calcium carbonate (for example, heavy calcium carbonate, light calcium carbonate, white sinter), magnesium silicate (for example, talc), mica, clay, mica powder, bentonite (for example, organic Bentonite etc.), silica, alumina, aluminum hydroxide, aluminum silicate, titanium oxide, carbon black (eg insulating carbon black, acetylene black etc.), aluminum powder, glass balloon and the like.
- the fillers can be used alone or in combination of two or more.
- a hollow filler having a small specific gravity such as a glass balloon, the weight of the reinforcing layer can be reduced without using a foaming agent.
- calcium carbonate is used.
- anti-aging agent examples include amine-ketone series, aromatic secondary amine series, phenol series, benzimidazole series (eg 2-mercaptobenzimidazole etc.), thiourea series, phosphorous acid series and the like.
- Antiaging agents can be used alone or in combination of two or more. A benzimidazole type is preferable.
- the addition ratio of the additive is, in particular, 1 to 200 parts by weight, for example, 1 to 200 parts by weight, for example, 0.1 to 5 parts by weight for the anti-aging agent, relative to 100 parts by weight of the polymer.
- an adhesive composition can be prepared by mix
- a known solvent for example, toluene, etc.
- water in the above-described blending ratio to prepare a solution or dispersion, and the resulting solution or dispersion is applied to the surface of the constraining layer.
- a method of drying after coating can be mentioned.
- the obtained solution or dispersion is applied to the surface of a release film, which will be described later, and then dried to form a reinforcing layer, and then the reinforcing layer is transferred to the surface of the constraining layer (transfer method) ).
- the above-described components (excluding the above-described solvent and water) are mixed with, for example, a mixing roll, a pressure type
- the kneaded product is formed into a sheet by calender molding, extrusion molding or press molding, and a reinforcing layer is formed.
- a method of laminating on the surface is also included.
- the kneaded product is placed between a constraining layer and a release film (described later), and then rolled into a sheet by, for example, press molding.
- a method in which the formed reinforcing layer is laminated on the surface of the release film, and then the reinforcing layer is transferred to the surface of the constraining layer.
- the thickness of the reinforcing layer formed in this way is, for example, 0.02 to 3.0 mm, preferably 0.03 to 1.3 mm.
- the thickness of the reinforcing layer can be set to, for example, 0.2 to 1.0 mm, preferably 0.5 to 0.9 mm.
- the reinforcing layer formed as described above has a storage elastic modulus (G ′) at 25 ° C. of, for example, 500 kPa or more, preferably 1500 kPa or more, and usually 200000 kPa or less, preferably It is 20000 kPa or less.
- G ′ storage elastic modulus
- the reinforcing property may not be sufficiently improved.
- the storage layer has a storage modulus (G ′) measured at 80 ° C. of, for example, 1000 kPa or less, preferably 500 kPa or less, and usually 100 kPa or more.
- G ′ storage modulus
- the storage elastic modulus at 80 ° C. is not within the above range, the resin molded product and the reinforcing layer may not be firmly adhered.
- the storage elastic modulus (G ′) at 25 ° C. and 80 ° C. will be described in detail in Examples, but a dynamic viscoelasticity measuring device (measurement conditions: initial strain 0.1%, temperature rising rate 5 ° C./min, frequency) 1 Hz).
- the thickness of the reinforcing sheet for resin molded product thus obtained is, for example, 0.25 to 5.0 mm, preferably 0.4 to 2.3 mm. Further, the thickness of the reinforcing sheet for resin molded product can be set to, for example, 0.3 to 3 mm, preferably 0.3 to 1.3 mm.
- the thickness of the reinforcing sheet for resin molded product exceeds the above range, it may be difficult to reduce the weight of the reinforcing sheet for resin molded product, and the manufacturing cost may increase. If the thickness of the reinforcing sheet for resin molded product is less than the above range, the reinforcing property may not be sufficiently improved.
- the obtained reinforcing sheet for a resin molded product is separated on the surface of the reinforcing layer (the surface on the side opposite to the back surface on which the constraining layer is pasted), if necessary, until it is actually used.
- a mold film (separator) can also be pasted.
- release film examples include known release films such as synthetic resin films such as polyethylene film, polypropylene film, and PET film.
- the thus formed reinforcing sheet for resin molded article (reinforcing layer thereof) is attached to a polypropylene plate having a thickness of 2.0 mm, and the bending strength at 1 mm displacement after heating at 80 ° C. for 10 minutes is 3N or more, preferably Is 3.5N or more, more preferably 4N or more, usually 20N or less, preferably 10N or less, and the maximum bending strength is 30N or more, preferably 35N or more, more preferably 40N or more, 200N or less, preferably 100N or less.
- the bending strength and maximum bending strength of the above-mentioned 1 mm displacement were obtained by externally processing a polypropylene plate having a thickness of 2.0 mm reinforced with a reinforcing sheet for resin molded product into a size of 150 mm length ⁇ 25 mm width.
- the distance between the fulcrums was set to 100 mm using a universal testing machine, and the center of the test piece (length direction and width direction center) was a polypropylene plate at a speed of 50 mm / min with a 10 mm diameter indenter. It is measured by a three-point bending test pressing from the side.
- the reinforcing sheet for resin molded product is attached to the polypropylene plate, the reinforcing layer and the polypropylene plate are brought into contact with each other.
- the bending strength of 1 mm displacement is the bending strength (strength) when the indenter is displaced by 1 mm from the start of pressing, and the maximum bending strength is the maximum bending strength (strength) between when pressing starts and when the specimen breaks. It is.
- the resin molded product can be sufficiently reinforced.
- the reinforcing sheet for resin molded article has an adhesive force A 0 to the polypropylene plate measured by a 90-degree peel test at a peeling rate of 300 mm / min after the reinforcing layer is attached to the polypropylene plate at room temperature (25 ° C.).
- a 0 to the polypropylene plate measured by a 90-degree peel test at a peeling rate of 300 mm / min after the reinforcing layer is attached to the polypropylene plate at room temperature (25 ° C.).
- 0.3 N / 25 mm or more preferably 1.0 N / 25 mm or more, further 3.0 N / 25 mm or more, further 5.0 N / 25 mm or more, 10 N / 25 mm or more, or 15 N / 25 mm.
- 20 N / 25 mm or more is preferable, and usually 40 N / 25 mm or less, preferably 30 N / 25 mm or less.
- the adhesive strength A 0 described above is defined as a normal temperature the adhesive force A 0.
- Ambient temperature at the time the adhesive force A 0 is measured in accordance with JIS Z0237 (2000 years).
- the reinforcing layer exhibits a slight adhesiveness (fine tackiness), so that it can be used at the normal temperature before heating.
- the reinforcing sheet can be securely attached to the resin molded product.
- the reinforcing sheet for a resin molded article is obtained by adhering a reinforcing layer to a polypropylene plate at room temperature, heating at 80 ° C. for 10 minutes, and then adhering strength A to the polypropylene plate measured by a 90 ° peel test at a peeling rate of 300 mm / min. 10 m is, for example, 15 N / 25 mm or more, preferably 20 N / 25 mm or more, more preferably 25 N / 25 mm or more, more preferably 30 N / 25 mm or more, and further preferably 40 N / 25 mm or more. 25 mm or less, preferably 100 N / 25 mm or less.
- the adhesive strength A 10 m as described above is defined as a post-heating adhesive strength A 10 m of 80 ° C..
- the adhesive strength A 10 m after heating at 80 ° C. is measured according to JIS Z0237 (2000).
- the adhesive strength A 10 m after heating at 80 ° C. is within the above-described range, the constraining layer and the resin molded product are more firmly adhered by the reinforcing layer by heating at a relatively low temperature (80 ° C.). Can do.
- the reinforcing sheet for a resin molded product has a high temperature, specifically, adhesive strength after heating to 100 ° C., specifically, first, the reinforcing layer is attached to a polypropylene plate at room temperature (25 ° C.) After heating at 80 ° C. for 10 minutes and then heating at 100 ° C.
- the adhesive strength A 1h to the polypropylene plate measured by a 90-degree peel test at a peeling rate of 300 mm / min is, for example, 50 N / 25 mm or more, preferably Is preferably 60 N / 25 mm or more, more preferably 65 N / 25 mm or more, further 70 N / 25 mm or more, more preferably 75 N / 25 mm or more, and further preferably 80 N / 25 mm or more, and usually 300 N / 25 mm or less, preferably Is 200 N / 25 mm or less.
- the adhesive force A 1h described above is defined as 1 hour post-heating adhesive force A 1h of 100 ° C..
- the above-mentioned adhesive strength A 1h after heating at 100 ° C. for 1 hour is measured according to JIS Z0237 (2000).
- the initial adhesive strength can be kept high when placed in a high temperature atmosphere, and the initial superiority in a high temperature atmosphere can be maintained. Reinforcing properties can be ensured.
- the reinforcing sheet for resin molded product is first peeled off by sticking the reinforcing layer to a polypropylene plate at room temperature (25 ° C.), heating them at 80 ° C. for 10 minutes, and then heating them at 100 ° C. for 1000 hours.
- the adhesive strength A 1000h for a polypropylene plate measured by a 90 degree peel test at a speed of 300 mm / min is, for example, 45 N / 25 mm or more, preferably 55 N / 25 mm or more, more preferably 60 N / 25 mm or more, and further 70 N / 25 mm or more, more preferably 80 N / 25 mm or more, further 90 N / 25 mm or more, more preferably 100 N / 25 mm or more, and usually 250 N / 25 mm or less, preferably 200 N / 25 mm or less, more preferably 125 N. / 25 mm or less.
- the adhesive force A 1000h as described above is defined as 1000 hours post-heating adhesive force A 1000h of 100 ° C..
- the adhesive strength A 1000h after heating at 100 ° C. for 1000 hours is within the above-mentioned range, it is possible to prevent a decrease in adhesive strength after a long time when placed in a high temperature atmosphere. It is possible to prevent a decrease in reinforcement after a long period of time.
- the reinforcing sheet for resin molded product has a ratio of the adhesive strength A 1000h to the adhesive strength A 1h , that is, the high temperature (100 ° C.) adhesive retention rate R ((adhesive strength A 1000h / adhesive strength A 1h ) ⁇ 100) 80% or more, preferably 85% or more, more preferably 90% or more, further 100% or more, further 110% or more, further 120% or more, further 135% or more, Is preferably 150% or more, and usually 500% or less.
- each adhesive force of the above-mentioned reinforcing sheet for a resin molded product is substantially the same as each adhesive force of the corresponding reinforcing layer.
- the reinforcing sheet for resin molded products of the present invention is used for reinforcing resin molded products.
- the resin molded product is not particularly limited as long as it is a resin molded product that needs reinforcement, and examples thereof include resin molded products used in various industrial products.
- resin which forms a resin molded product low polar resin, such as olefin resin, etc. are mentioned, for example.
- olefin resin examples include polypropylene and polyethylene, and preferably polypropylene.
- FIG. 1 is an explanatory diagram showing an embodiment of a method for reinforcing a resin molded product according to the present invention, in which a reinforcing sheet for a resin molded product according to the present invention is attached to a resin molded product and is reinforced by heating.
- (A) is a step of preparing a reinforcing sheet for a resin molded product and peeling off the release film
- (b) is a step of attaching the reinforcing sheet for a resin molded product to the resin molded product and heating it. Show.
- the reinforcing sheet for resin molded product of the present invention is reinforced by sticking the reinforcing sheet for resin molded product to the resin molded product and heating it. An embodiment will be described.
- the reinforcing sheet 1 for a resin molded product is formed by laminating a reinforcing layer 2 on a constraining layer 3 and the surface of the reinforcing layer 2 (the opposite side to the back surface on which the constraining layer 3 is laminated). If necessary, a release film 6 is attached to the surface.
- the resin molded product 4 is used for the above-described various industrial products, and is formed, for example, in a plate shape, and more specifically, appears in the appearance. It is formed to have an outer surface 7 and an inner surface 8 that faces inward and does not appear in appearance.
- the release film 6 is peeled from the surface of the reinforcement layer 2
- the surface of the reinforcing layer 2 is brought into contact with the inner surface 8 of the resin molded product 4 and is pressure-bonded as necessary.
- the pressure is applied at a pressure of about 0.15 to 10 MPa.
- heating can be performed together with pressurization. That is, the reinforcing sheet for resin molded product 1 is heated in advance, and then the heated reinforcing sheet for resin molded product 1 is attached to the resin molded product 4.
- the conditions for thermocompression bonding are, for example, a temperature of 80 ° C. or higher, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and usually lower than the heat resistant temperature of the resin molded product 4. It is 130 ° C. or lower, preferably 30 to 120 ° C., more preferably 80 to 110 ° C.
- the heating temperature is 80 ° C. or more, preferably 90 ° C. or more, more preferably 100 ° C. or more, and usually the heat resistant temperature of the resin molded product 4 or less. Specifically, for example, 130 ° C. or less, preferably 30 to 120 ° C, more preferably 80 to 110 ° C.
- the heating time is, for example, 0.5 to 20 minutes, preferably 1 to 10 minutes.
- the resin molded product 4 and the constraining layer 3 cannot be sufficiently adhered, or the reinforcing property at the time of reinforcement of the resin molded product 4 is sufficiently improved. It may not be possible. When the heating temperature and the heating time exceed the above ranges, the resin molded product 4 may be deteriorated or melted.
- the heating of the resin molded product 4 described above is carried out by putting the resin molded product 4 on which the reinforcing sheet 1 for resin molded product is adhered into a drying furnace in the drying process of manufacturing the resin molded product 4.
- the reinforcing sheet 1 for the resin molded product is used by using a partial heating device such as a heat gun instead of the above-described drying furnace. Heat.
- the resin molded product reinforcing sheet 1 is bonded to the resin molded product 4 and the resin molded product reinforcing sheet 1 and / or the resin molded product 4 is heated, whereby the resin molded product reinforcing sheet 1 is resin molded.
- the reinforcement structure of the resin molded product 4 in which the reinforcing sheet 1 for resin molded products is reinforced is formed in close contact with the product 4.
- the restraining layer 3 and the resin molded product 4 can be firmly adhered to each other by the reinforcing layer 2 by heating at a relatively low temperature.
- the rigidity of the reinforcing sheet for resin molded product 1 can be improved. Therefore, the resin molded product 4 can be reliably reinforced by the resin molded product reinforcing sheet 1.
- the reinforcing sheet 1 for a resin molded product has a simple configuration including the constraining layer 3 and the reinforcing layer 2, the resin molded product 4 can be reinforced while reducing the thickness and weight.
- the high-temperature adhesive retention rate R of the reinforcing layer 2 is within a specific range, so that the constraining layer 3 and the resin molded product 4 are formed by heating at a relatively low temperature as described above. Even after a long period of time in a high temperature (high temperature lower than the heat resistance temperature of the resin molded product 4) atmosphere after the adhesion, the adhesion between the constraining layer 3 and the resin molded product 6 can be maintained well, or The adhesion can be improved.
- the reinforcing layer 2 is formed from only one sheet made of the pressure-sensitive adhesive composition. For example, as shown by a broken line in FIG. It can also be interposed.
- Nonwoven fabric 5 may be the same as the nonwoven fabric described above.
- the thickness of the nonwoven fabric 5 is, for example, 0.01 to 0.3 mm.
- the first reinforcing layer is laminated on the surface of the constraining layer 3, and the surface of the first reinforcing layer (the constraining layer 3).
- the nonwoven fabric 5 is laminated on the surface opposite to the back surface on which the first reinforcing layer is laminated, and then the second reinforcement is applied to the surface of the nonwoven fabric 5 (the surface opposite to the back surface on which the first reinforcing layer is laminated). Laminate the layers.
- the nonwoven fabric 5 is sandwiched from both the front and back sides of the nonwoven fabric 5 by the first reinforcing layer and the second reinforcing layer. Specifically, first, the first reinforcing layer and the second reinforcing layer are respectively formed on the surfaces of the two release films 6, and then the first reinforcing layer is transferred to the back surface of the nonwoven fabric 5. The layer is transferred to the surface of the nonwoven fabric 5.
- the reinforcing layer 2 can be easily formed with a thick thickness according to the strength of the resin molded product 4 to be reinforced.
- the kneaded product of the prepared pressure-sensitive adhesive composition is sandwiched between a resin-impregnated glass cloth (restraint layer) having a thickness of 0.18 mm impregnated with an epoxy resin and a release film, and press molding at 120 ° C.
- the kneaded product was rolled into a sheet to prepare a reinforcing sheet for a resin molded product having a thickness of 0.8 mm. (See FIG. 1 (a)). Note that the thickness of the reinforcing layer was 0.62 mm.
- Comparative Example 2 5 parts by weight of dicyandiamide (DCDA, curing agent) and 2 parts by weight of an imidazole compound (2MAOK, curing agent, manufactured by Shikoku Kasei Co., Ltd.) with respect to 100 parts by weight of bisphenol A type epoxy resin (# 834, Japan Epoxy Resin) 100 parts by weight of talc (trade name “imported talc”, magnesium silicate, manufactured by Sobue clay), 10 parts by weight of organite (organic bentonite, manufactured by Nippon Organic Clay), carbon black (Asahi # 50, insulating carbon black, Asahi A kneaded product of the pressure-sensitive adhesive composition was prepared by blending 0.5 part by weight (made by Carbon Co., Ltd.) and kneading with a mixing roll preheated to 80 ° C.
- the kneaded product of the prepared pressure-sensitive adhesive composition was press-molded to form a reinforcing layer having a thickness of 0.30 mm.
- a reinforcing layer was laminated on the surface of a resin-impregnated glass cloth having a thickness of 0.18 mm impregnated with an epoxy resin to prepare a reinforcing sheet for a resin molded product having a thickness of 0.48 mm.
- a test piece was obtained by sticking a reinforcing sheet for resin molded product to a polypropylene plate having a thickness of 2.0 mm, and then the test piece was placed between fulcrums using a universal testing machine (manufactured by Minebea). The distance was 100 mm, and the center (length direction and width direction center) of the test piece was pressed from the polypropylene plate side at a speed of 50 mm / min with an indenter having a diameter of 10 mm.
- the reinforcing layer and the polypropylene plate were brought into contact with each other.
- the bending strength and the maximum bending strength at a displacement of 1 mm are as high as 3 N or more and 30 N or more, respectively.
- Dynamic viscoelasticity measuring device ARES, manufactured by Rheometric Scientific Inc. Jig: Parallel plate Sample thickness approx. 1.0mm Diameter 7.9mm Measurement conditions: Initial strain 0.1% Temperature rising rate 5 ° C / min Frequency 1Hz 3) Adhesive strength of reinforcing layer (adhesive strength A 0 at normal temperature, adhesive strength A 10 m after heating at 80 ° C., adhesive strength A xh after heating at 100 ° C.) Only the reinforcing layer formed in each example and each comparative example was measured for each adhesive force described below with respect to a polypropylene plate by a 90-degree peel test of JIS Z0237 (2000) at a peeling speed of 300 mm / min.
- the heating time at 100 ° C. described above was 95 hours (only Examples 1 and 2 and Comparative Example 1), 166 hours (only Examples 1 and 2 and Comparative Example 1), and 287 hours (Examples 1 to 3 and Comparative Example 1 only) 475 hours (Examples 1 to 3 and Comparative Example 1 only), 744 hours (Examples 1 and 2 and Comparative Example 1 only) and 1000 hours (Examples 1 to 10 and Comparative Example 1)
- the adhesive strength A 95h , the adhesive strength A 166 h , the adhesive strength A 287 h , the adhesive strength A 475 h , the adhesive strength A 744 h and the adhesive strength A 1000 h were measured by changing each.
- FIG. 2 shows the relationship between the heating time at 100 ° C. and the adhesive strength (adhesive strength A xh after high temperature heating) for Examples 1 to 3 and Comparative Example 1.
- the high-temperature heating adhesive strength A xh greatly decreases as the heating time elapses, and after 1000 hours of heating, it is less than 45 N / 25 mm. Yes, the high temperature adhesion retention R is less than 80%.
- the adhesive strength A xh after high-temperature heating did not substantially decrease even when the heating time elapsed.
- all of them are 45 N / 25 mm or more after heating for 1000 hours, and the high-temperature adhesive retention ratio R is as high as 80% or more.
- the adhesive strength A 1000h after heating at 100 ° C. for 1000 hours was higher than the adhesive strength A 1h after heating at 100 ° C. for 1 hour, Specifically, all are 60 N / 25 mm or more, and the high temperature adhesion retention R is as high as 115% or more.
- each component of the reinforcing layer (adhesive composition) in Table 1 indicates the number of blended parts.
- H1041 Trade name “Tuftec H1041”, styrene-ethylene-butylene-styrene block copolymer, styrene / ethylene and butadiene ratio: 30 wt% / 70 wt%, MFR (190 ° C., 2.16 kg): 0.3 g / 10 minutes, MFR (200 ° C., 5 kg): 3 g / 10 minutes, manufactured by Asahi Kasei Chemicals Corporation H1052: trade name “Tuftec H1052”, styrene-ethylene-butylene-styrene block copolymer, styrene / ethylene-butadiene ratio: 20 weight % / 80% by weight, MFR (190 ° C., 2.16 kg): 3 g / 10 min, MFR (200 ° C., 5 kg): 10 g / 10 min, bisphenol A type epoxy resin manufactured by Asahi Kasei Chemicals: trade name
- Clearon P85 trade name, hydrogenated terpene resin ( Rupen resin), softening point (ring-and-ball method) 85 ° C., weight average molecular weight 630 (GPC method based on standard PS conversion), glass transition point (DSC method) 28 ° C., YShara Chemical YS Polystar U115: trade name, terpene phenol Copolymer (terpene resin), softening point (ring ball method) 115 ° C., glass transition point (DSC method) 57 ° C., weight average molecular weight 670 (GPC method based on standard PS conversion), Yashara Chemical Co., Ltd.
- PetroTac 90HM product Name, hydrocarbon petroleum resin, softening point (ring and ball method) 88 ° C., manufactured by Tosoh Corporation Heavy calcium carbonate: manufactured by Maruo Calcium Co., Ltd.
- Asahi # 50 Product name, carbon black, manufactured by Asahi Carbon Co., Ltd. ”, Magnesium silicate, Organite made by Sobueclay Co., Ltd .: Trade name, organic bentonite, NOCRACK made by Nippon Organic Clay Co., Ltd.
- B Trade name, 2-mercaptobenzimidazole, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
- DCDA Dicyandiamide
- foaming agent Imidazole compound Trade name “2MAOK”
- curing agent manufactured by Shikoku Kasei Co., Ltd.
- the reinforcing sheet for resin molded products of the present invention is used for reinforcing various resin molded products.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
100℃の1000時間加熱後粘着力A1000h:前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱し、その後、100℃で1000時間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力
100℃の1時間加熱後粘着力A1h:前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱し、その後、100℃で1時間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力
また、本発明の樹脂成形品用補強シートでは、前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力A10mが、15N/25mm以上であることが好適である。
100℃の1000時間加熱後粘着力A1000h:前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱し、その後、100℃で1000時間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力
100℃の1時間加熱後粘着力A1h:前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱し、その後、100℃で1時間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力
また、本発明の樹脂成形品の補強構造は、前記樹脂成形品用補強シートを、予め、80℃以上に加熱し、次いで、前記樹脂成形品用補強シートを前記樹脂成形品に貼着することが好適である。
100℃の1000時間加熱後粘着力A1000h:前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱し、その後、100℃で1000時間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力
100℃の1時間加熱後粘着力A1h:前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱し、その後、100℃で1時間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力
また、本発明の樹脂成形品の補強方法は、前記樹脂成形品用補強シートを前記樹脂成形品に貼着する工程では、前記樹脂成形品用補強シートを、予め、80℃以上に加熱し、次いで、前記樹脂成形品用補強シートを前記樹脂成形品に貼着することが好適である。
表1に示す配合処方において、各成分を重量部基準で配合して、120℃に予め加熱したミキシングロールで混練することにより、粘着剤組成物の混練物を調製した。
ビスフェノールA型エポキシ樹脂(♯834、ジャパンエポキシレジン社製)100重量部に対して、ジシアンジアミド(DCDA、硬化剤)5重量部およびイミダゾール化合物(2MAOK、硬化剤、四国化成社製)2重量部、タルク(商品名「輸入タルク」、ケイ酸マグネシウム、ソブエクレー社製)100重量部、オルガナイト(有機ベントナイト、日本有機粘土社製)10重量部、カーボンブラック(旭♯50、絶縁性カーボンブラック、旭カーボン社製)0.5重量部を配合し、80℃に予め加熱したミキシングロールで混練することにより、粘着剤組成物の混練物を調製した。
得られた各実施例および各比較例について、曲げ強度、貯蔵弾性率および粘着力を次のように評価した。その結果を表1に示す。
1)樹脂成形品用補強シートの曲げ強度
各実施例および各比較例の樹脂成形品用補強シートを、厚み2.0mmのポリプロピレン板に貼着し、これらを80℃で10分間加熱した後、三点曲げ試験により、1mm変位時の曲げ強度および最大曲げ強度を、それぞれ測定した。
2)補強層の貯蔵弾性率(G’)
実施例1~3、比較例1および2において形成した補強層のみの、25℃および80℃における貯蔵弾性率(G’)を、動的粘弾性測定装置により測定した。
使用治具 :パラレルプレート
サンプル厚さ約1.0mm
直径7.9mm
測定条件 :初期ひずみ0.1%
昇温速度5℃/分
周波数1Hz
3)補強層の粘着力(常温時粘着力A0、80℃の加熱後粘着力A10m、100℃の加熱後粘着力Axh)
各実施例および各比較例において形成した補強層のみを、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験によって、ポリプロピレン板に対する次に述べる各粘着力を測定した。
(i) 常温時粘着力A0
まず、実施例および各比較例の補強層のみを、常温(25℃)でポリプロピレン板に貼着し、その後、ポリプロピレン板に対する粘着力(常温時粘着力)A0を測定した。
(ii) 80℃の加熱後粘着力A10m
まず、各実施例および各比較例の補強層のみを、常温(25℃)でポリプロピレン板に貼着し、次いで、それらを80℃で10分間加熱した後に、ポリプロピレン板に対する粘着力(80℃の10分間加熱後粘着力)A10mを測定した。
(iii) 100℃の加熱後粘着力
まず、実施例1~10および比較例1の補強層のみを、常温(25℃)でポリプロピレン板に貼着し、次いで、それらを80℃で10分間加熱し、その後、100℃で1時間加熱した後に、ポリプロピレン板に対する粘着力(100℃の1時間加熱後粘着力)A1hを測定した。
H1052:商品名「タフテックH1052」、スチレン-エチレン-ブチレン-スチレンブロック共重合体、スチレン/エチレン・ブタジエン比:20重量%/80重量%、MFR(190℃、2.16kg):3g/10分、MFR(200℃、5kg):10g/10分、旭化成ケミカルズ社製
ビスフェノールA型エポキシ樹脂:商品名「♯834」、外観:常温で液状、70%ブチルカルビトール溶液粘度:P~U、ジャパンエポキシレジン社製
T420:商品名「アサプレンT420」、スチレン/ブタジエン比:30重量%/70重量%、MFR(190℃、2.16kg):1.1g/10分、MFR(200℃、5kg):6.5g/10分、旭化成ケミカルズ社製
T432:商品名「アサプレンT432」、スチレン/ブタジエン比:30重量%/70重量%、MFR(190℃、2.16kg):0g/10分、MFR(200℃、5kg):1g/10分未満、旭化成ケミカルズ社製
アルコンM100:商品名、脂環族飽和炭化水素系樹脂、軟化点(環球法)100℃、荒川化学工業社製
アルコンP100:商品名、脂環族飽和炭化水素系樹脂、軟化点(環球法)100℃、荒川化学工業社製
クリアロンP85:商品名、水素添加テルペン樹脂(テルペン系樹脂)、軟化点(環球法)85℃、重量平均分子量630(標準PS換算に基づくGPC法)、ガラス転移点(DSC法)28℃、ヤスハラケミカル社製
YSポリスターU115:商品名、テルペンフェノール共重合体(テルペン系樹脂)、軟化点(環球法)115℃、ガラス転移点(DSC法)57℃、重量平均分子量670(標準PS換算に基づくGPC法)、ヤスハラケミカル社製
ペトロタック90HM:商品名、炭化水素系石油樹脂、軟化点(環球法)88℃、東ソー社製
重質炭酸カルシウム:丸尾カルシウム社製
旭♯50:商品名、カーボンブラック、旭カーボン社製
タルク:商品名「輸入タルク」、ケイ酸マグネシウム、ソブエクレー社製
オルガナイト:商品名、有機ベントナイト、日本有機粘土社製
ノクラックMB:商品名、2-メルカプトベンズイミダゾール、大内新興化学工業社製
DCDA:ジシアンジアミド、発泡剤
イミダゾール化合物:商品名「2MAOK」、硬化剤、四国化成社製
なお、上記説明は、本発明の例示の実施形態として提供したが、これは単なる例示にすぎず、限定的に解釈してはならない。当該技術分野の当業者によって明らかな本発明の変形例は、後記の特許請求の範囲に含まれるものである。
Claims (15)
- 拘束層と、前記拘束層に積層される補強層とを備える樹脂成形品用補強シートであって、
前記樹脂成形品用補強シートを厚み2.0mmのポリプロピレン板に貼着し、80℃で10分間加熱後の1mm変位の曲げ強度が3N以上、かつ、最大曲げ強度が30N以上であり、下記の高温粘着保持率Rが、80%以上であることを特徴とする、樹脂成形品用補強シート。
高温粘着保持率R=(100℃の1000時間加熱後粘着力A1000h/100℃の1時間加熱後粘着力A1h)×100
100℃の1000時間加熱後粘着力A1000h:前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱し、その後、100℃で1000時間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力
100℃の1時間加熱後粘着力A1h:前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱し、その後、100℃で1時間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力 - 前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力A10mが、15N/25mm以上であることを特徴とする、請求項1に記載の樹脂成形品用補強シート。
- 100℃の1時間加熱後粘着力A1hが、50N/25mm以上であることを特徴とする、請求項1に記載の樹脂成形品用補強シート。
- 前記補強層は、25℃における貯蔵弾性率が500kPa以上、かつ、80℃における貯蔵弾性率が500kPa以下であることを特徴とする、請求項1に記載の樹脂成形品用補強シート。
- 剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する常温時粘着力A0が、0.3N/25mm以上であることを特徴とする、請求項1に記載の樹脂成形品用補強シート。
- 前記補強層が、熱接着型の粘着剤組成物から形成されていることを特徴とする、請求項1に記載の樹脂成形品用補強シート。
- 前記粘着剤組成物が、共役ジエン類を含む単量体の重合体の水素添加物を含有していることを特徴とする、請求項6に記載の樹脂成形品用補強シート。
- 前記粘着剤組成物が、さらに、粘着付与剤を含有していることを特徴とする、請求項7に記載の樹脂成形品用補強シート。
- 前記粘着付与剤が、脂環族飽和炭化水素系樹脂を含有していることを特徴とする、請求項8に記載の樹脂成形品用補強シート。
- 前記粘着付与剤が、テルペン系樹脂をさらに含有していることを特徴とする、請求項9に記載の樹脂成形品用補強シート。
- 前記粘着付与剤の配合割合が、前記水素添加物100重量部に対して、40~200重量部であることを特徴とする、請求項8に記載の樹脂成形品用補強シート。
- 拘束層と、前記拘束層に積層される補強層とを備える樹脂成形品用補強シートを樹脂成形品に貼着し、次いで、80℃以上に加熱して、前記樹脂成形品用補強シートを前記樹脂成形品に密着させることにより、前記樹脂成形品が補強されており、
前記樹脂成形品用補強シートを厚み2.0mmのポリプロピレン板に貼着し、80℃で10分間加熱後の1mm変位の曲げ強度が3N以上、かつ、最大曲げ強度が30N以上であり、下記の高温粘着保持率Rが、80%以上であることを特徴とする、樹脂成形品の補強構造。
高温粘着保持率R=(100℃の1000時間加熱後粘着力A1000h/100℃の1時間加熱後粘着力A1h)×100
100℃の1000時間加熱後粘着力A1000h:前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱し、その後、100℃で1000時間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力
100℃の1時間加熱後粘着力A1h:前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱し、その後、100℃で1時間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力 - 前記樹脂成形品用補強シートを、予め、80℃以上に加熱し、次いで、前記樹脂成形品用補強シートを前記樹脂成形品に貼着することを特徴とする、請求項12に記載の樹脂成形品の補強構造。
- 拘束層と、前記拘束層に積層される補強層とを備える樹脂成形品用補強シートを樹脂成形品に貼着する工程、および、
前記樹脂成形品用補強シートおよび/または前記樹脂成形品を80℃以上に加熱して、前記樹脂成形品用補強シートを前記樹脂成形品に密着させることにより、前記樹脂成形品を補強する工程
を備え、
前記樹脂成形品用補強シートを厚み2.0mmのポリプロピレン板に貼着し、80℃で10分間加熱後の1mm変位の曲げ強度が3N以上、かつ、最大曲げ強度が30N以上であり、下記の高温粘着保持率Rが、80%以上であることを特徴とする、樹脂成形品の補強方法。
高温粘着保持率R=(100℃の1000時間加熱後粘着力A1000h/100℃の1時間加熱後粘着力A1h)×100
100℃の1000時間加熱後粘着力A1000h:前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱し、その後、100℃で1000時間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力
100℃の1時間加熱後粘着力A1h:前記補強層をポリプロピレン板に貼着し、80℃で10分間加熱し、その後、100℃で1時間加熱後に、剥離速度300mm/分でJIS Z0237(2000年)の90度ピール試験により測定されるポリプロピレン板に対する粘着力 - 前記樹脂成形品用補強シートを前記樹脂成形品に貼着する工程では、前記樹脂成形品用補強シートを、予め、80℃以上に加熱し、次いで、前記樹脂成形品用補強シートを前記樹脂成形品に貼着することを特徴とする、請求項14に記載の樹脂成形品の補強方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2011800142280A CN102811859A (zh) | 2010-03-18 | 2011-03-15 | 树脂成型品用增强片、树脂成型品的增强结构及增强方法 |
KR1020127024159A KR20130006450A (ko) | 2010-03-18 | 2011-03-15 | 수지 성형품용 보강 시트, 수지 성형품의 보강 구조 및 보강 방법 |
US13/635,878 US20130011667A1 (en) | 2010-03-18 | 2011-03-15 | Reinforcing sheet for resin molded article, reinforced structure of resin molded article, and reinforcing method |
EP11756324.7A EP2548737B1 (en) | 2010-03-18 | 2011-03-15 | Reinforcing sheet for resin molded article, reinforced structure of resin molded article, and reinforcing method |
US14/149,517 US20140116619A1 (en) | 2010-03-18 | 2014-01-07 | Reinforcing sheet for resin molded article, reinforced structure of resin molded article, and reinforcing method |
US14/149,510 US9114599B2 (en) | 2010-03-18 | 2014-01-07 | Reinforcing sheet for resin molded article, reinforced structure of resin molded article, and reinforcing method |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-062029 | 2010-03-18 | ||
JP2010062029 | 2010-03-18 | ||
JP2011-051462 | 2011-03-09 | ||
JP2011051462A JP5694009B2 (ja) | 2010-03-18 | 2011-03-09 | 樹脂成形品用補強シート、樹脂成形品の補強構造および補強方法 |
Related Child Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/635,878 A-371-Of-International US20130011667A1 (en) | 2010-03-18 | 2011-03-15 | Reinforcing sheet for resin molded article, reinforced structure of resin molded article, and reinforcing method |
US14/149,510 Division US9114599B2 (en) | 2010-03-18 | 2014-01-07 | Reinforcing sheet for resin molded article, reinforced structure of resin molded article, and reinforcing method |
US14/149,517 Division US20140116619A1 (en) | 2010-03-18 | 2014-01-07 | Reinforcing sheet for resin molded article, reinforced structure of resin molded article, and reinforcing method |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011115140A1 true WO2011115140A1 (ja) | 2011-09-22 |
Family
ID=44649224
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/056116 WO2011115140A1 (ja) | 2010-03-18 | 2011-03-15 | 樹脂成形品用補強シート、樹脂成形品の補強構造および補強方法 |
Country Status (6)
Country | Link |
---|---|
US (3) | US20130011667A1 (ja) |
EP (1) | EP2548737B1 (ja) |
JP (1) | JP5694009B2 (ja) |
KR (1) | KR20130006450A (ja) |
CN (1) | CN102811859A (ja) |
WO (1) | WO2011115140A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012043275A1 (ja) * | 2010-09-30 | 2012-04-05 | 日東電工株式会社 | 金属板の補強方法および補強構造 |
US20150031839A1 (en) * | 2012-03-06 | 2015-01-29 | Sumitomo Rubber Industries, Ltd. | Hydrogenated branched conjugated diene copolymer, rubber composition and pneumatic tire |
US8962144B2 (en) | 2011-09-15 | 2015-02-24 | Nitto Denko Corporation | Reinforcing sheet for resin molded product, and structure and method for reinforcing resin molded product |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6311229B2 (ja) * | 2013-06-10 | 2018-04-18 | 三菱ケミカル株式会社 | 成形体の製造方法、および成形体 |
KR101912500B1 (ko) * | 2016-07-11 | 2018-10-26 | (주)엘지하우시스 | 자동차용 내장재 및 이의 제조방법 |
EP3533851B1 (en) | 2016-10-26 | 2024-07-03 | Riken Technos Corporation | Adhesive film |
WO2019225574A1 (ja) * | 2018-05-23 | 2019-11-28 | 東洋鋼鈑株式会社 | 熱可塑性樹脂フィルム、熱可塑性樹脂被覆金属板、及び熱可塑性樹脂被覆金属容器 |
JP2020012361A (ja) * | 2018-07-04 | 2020-01-23 | 株式会社ナベカヰ | 解体機のシリンダの搬送用固定治具、解体機の建築物解体作業現場における組立方法、及び分解方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06171001A (ja) * | 1992-12-10 | 1994-06-21 | Nippon Zeon Co Ltd | パネル補強用シート材料及びそれを用いた車輌外板パネル |
JP2002201300A (ja) * | 2000-12-28 | 2002-07-19 | Saitama Rubber Kogyo Kk | 架橋可能な熱可塑性樹脂組成物および樹脂組成物シート |
JP2002249738A (ja) * | 2001-02-26 | 2002-09-06 | Nitto Denko Corp | 剥離ライナー付き加熱接着シート |
JP2004115040A (ja) * | 2002-09-25 | 2004-04-15 | Dainippon Ink & Chem Inc | 容器および再封性包装容器 |
JP2005041210A (ja) | 2003-07-04 | 2005-02-17 | Nitto Denko Corp | 鋼板補強シート |
JP2007160895A (ja) * | 2005-12-16 | 2007-06-28 | Iida Sangyo Kk | 金属板用制振補強材 |
JP2008247028A (ja) * | 2007-03-08 | 2008-10-16 | Nitto Denko Corp | 補強シートおよび薄板の補強方法 |
JP2009039909A (ja) * | 2007-08-07 | 2009-02-26 | Toyota Motor Corp | 多層型鋼板補強材 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4578302A (en) | 1985-06-27 | 1986-03-25 | National Starch And Chemical Corporation | Reinforced tape laminates |
JP3604117B2 (ja) * | 1997-03-06 | 2004-12-22 | 株式会社クラレ | 熱可塑性重合体組成物 |
DE10127325A1 (de) * | 2001-06-06 | 2003-02-06 | Tesa Ag | Selbstklebender Schutzartikel für mechanisch stark beanspruchte lackierte Autobilteile |
US8017533B2 (en) | 2003-07-04 | 2011-09-13 | Nitto Denko Corporation | Steel plate reinforcing sheet |
JP2005097447A (ja) | 2003-09-25 | 2005-04-14 | Mikasa Seiyaku Co Ltd | 粘着剤及びそれを用いた貼付用温熱材 |
JP4808080B2 (ja) * | 2005-11-17 | 2011-11-02 | 日東電工株式会社 | 鋼板補強シート |
EP2012295A4 (en) * | 2006-04-24 | 2011-03-09 | Nitto Denko Corp | REINFORCEMENT SHEET FOR IMAGE DISPLAY, IMAGE DISPLAY AND REINFORCEMENT METHOD THEREOF |
JP5489571B2 (ja) * | 2008-09-22 | 2014-05-14 | 日東電工株式会社 | 樹脂成形品用補強シート、樹脂成形品の補強構造および補強方法 |
JP2011032986A (ja) | 2009-08-05 | 2011-02-17 | Nitto Denko Corp | 風力発電機ブレード用制振シート、風力発電機ブレードの制振構造、風力発電機および風力発電機ブレードの制振方法 |
-
2011
- 2011-03-09 JP JP2011051462A patent/JP5694009B2/ja active Active
- 2011-03-15 CN CN2011800142280A patent/CN102811859A/zh active Pending
- 2011-03-15 KR KR1020127024159A patent/KR20130006450A/ko not_active Application Discontinuation
- 2011-03-15 US US13/635,878 patent/US20130011667A1/en not_active Abandoned
- 2011-03-15 EP EP11756324.7A patent/EP2548737B1/en active Active
- 2011-03-15 WO PCT/JP2011/056116 patent/WO2011115140A1/ja active Application Filing
-
2014
- 2014-01-07 US US14/149,510 patent/US9114599B2/en active Active
- 2014-01-07 US US14/149,517 patent/US20140116619A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06171001A (ja) * | 1992-12-10 | 1994-06-21 | Nippon Zeon Co Ltd | パネル補強用シート材料及びそれを用いた車輌外板パネル |
JP2002201300A (ja) * | 2000-12-28 | 2002-07-19 | Saitama Rubber Kogyo Kk | 架橋可能な熱可塑性樹脂組成物および樹脂組成物シート |
JP2002249738A (ja) * | 2001-02-26 | 2002-09-06 | Nitto Denko Corp | 剥離ライナー付き加熱接着シート |
JP2004115040A (ja) * | 2002-09-25 | 2004-04-15 | Dainippon Ink & Chem Inc | 容器および再封性包装容器 |
JP2005041210A (ja) | 2003-07-04 | 2005-02-17 | Nitto Denko Corp | 鋼板補強シート |
JP2007160895A (ja) * | 2005-12-16 | 2007-06-28 | Iida Sangyo Kk | 金属板用制振補強材 |
JP2008247028A (ja) * | 2007-03-08 | 2008-10-16 | Nitto Denko Corp | 補強シートおよび薄板の補強方法 |
JP2009039909A (ja) * | 2007-08-07 | 2009-02-26 | Toyota Motor Corp | 多層型鋼板補強材 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012043275A1 (ja) * | 2010-09-30 | 2012-04-05 | 日東電工株式会社 | 金属板の補強方法および補強構造 |
US8962144B2 (en) | 2011-09-15 | 2015-02-24 | Nitto Denko Corporation | Reinforcing sheet for resin molded product, and structure and method for reinforcing resin molded product |
US20150031839A1 (en) * | 2012-03-06 | 2015-01-29 | Sumitomo Rubber Industries, Ltd. | Hydrogenated branched conjugated diene copolymer, rubber composition and pneumatic tire |
US10040877B2 (en) * | 2012-03-06 | 2018-08-07 | Sumitomo Rubber Industries, Ltd. | Hydrogenated branched conjugated diene copolymer, rubber composition and pneumatic tire |
US10759885B2 (en) | 2012-03-06 | 2020-09-01 | Sumitomo Rubber Industries, Ltd. | Hydrogenated branched conjugated diene copolymer, rubber composition and pneumatic tire |
Also Published As
Publication number | Publication date |
---|---|
JP2011213107A (ja) | 2011-10-27 |
EP2548737A4 (en) | 2014-05-14 |
US9114599B2 (en) | 2015-08-25 |
US20130011667A1 (en) | 2013-01-10 |
EP2548737B1 (en) | 2020-01-08 |
KR20130006450A (ko) | 2013-01-16 |
US20140120343A1 (en) | 2014-05-01 |
US20140116619A1 (en) | 2014-05-01 |
EP2548737A1 (en) | 2013-01-23 |
JP5694009B2 (ja) | 2015-04-01 |
CN102811859A (zh) | 2012-12-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5694009B2 (ja) | 樹脂成形品用補強シート、樹脂成形品の補強構造および補強方法 | |
JP5489571B2 (ja) | 樹脂成形品用補強シート、樹脂成形品の補強構造および補強方法 | |
KR101342715B1 (ko) | 금속판의 보강 방법 및 보강 구조 | |
JP5856803B2 (ja) | 接着性樹脂組成物、接着性樹脂成形体、及び接着性樹脂積層体 | |
JP4095972B2 (ja) | 自動車内装材用プレコート表皮材および自動車内装材の製造方法 | |
MXPA06013303A (es) | Lamina de refuerzo de placa de acero. | |
JP5755092B2 (ja) | 樹脂成形品用補強シート、樹脂成形品の補強構造および補強方法 | |
WO2012002076A1 (ja) | 熱伝導性補強シート、成形品およびその補強方法 | |
TW201144402A (en) | Method for binding substrate | |
JP5946254B2 (ja) | 樹脂成形品用補強シート、樹脂成形品の補強構造および補強方法 | |
JP4890380B2 (ja) | 多層型鋼板補強材 | |
JP7366647B2 (ja) | ホットメルト接着シート | |
JP2019172750A (ja) | 基材付き接着シート | |
JP6433097B2 (ja) | 接着性樹脂フィルム | |
JP2017025329A (ja) | 接着性樹脂フィルムの製造方法 | |
JP6006387B2 (ja) | 接着性樹脂フィルム、及び接着性樹脂積層体 | |
JP2024139562A (ja) | 樹脂組成物およびその利用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180014228.0 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11756324 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011756324 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20127024159 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13635878 Country of ref document: US |