JP2014168997A - Tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tire in which degree of freedom of designing a tire skeleton member itself can be maintained, weather fastness of a tire outer surface is improved, and both of suppressing tire weight increasing and maintaining appearance of a decorative part are achieved.SOLUTION: The tire comprises: a tire skeleton member 17 formed of a resin material and at least having a tread part and a bead part; and a coating layer 24 formed of a resin material and formed on the outside of the tire skeleton member 17 from the bead part to the tread part, and having a decorative part on its surface.

Description

  The present invention relates to a tire.

  Conventionally, a tire formed of rubber, an organic fiber material, and a steel member is known. In recent years, from the viewpoint of weight reduction and ease of recycling, it is required to use a thermoplastic polymer material such as a thermoplastic elastomer (TPE) or a thermoplastic resin as a tire frame member. For example, Patent Document 1 discloses that a tire frame member is formed by covering a bead core with a thermoplastic elastomer.

Japanese Patent Laid-Open No. 03-143701

  However, in Patent Document 1, the tire frame member is exposed at the side portion of the tire. In consideration of improving the weather resistance of the tire with the configuration of Patent Document 1, the material of the tire frame member itself must be changed, and the degree of freedom in design is reduced.

  The present invention has been made in consideration of the above facts, and while improving the weather resistance of the tire outer surface while maintaining the degree of freedom in designing the tire frame member itself, the weight of the tire is suppressed and added. It is an object of the present invention to provide a tire that can maintain the appearance of the decoration part.

  The tire according to claim 1 is made of a resin material, and is made of a resin material and a tire frame member having at least a tread portion and a bead portion, and is formed on the outer side of the tire frame member from the bead portion to the tread portion. And a coating layer having a decorative portion on the surface.

  In the tire according to claim 1, the outer surface from the bead portion to the tread portion of the tire frame member is covered with the coating layer. Therefore, the surface of the tire frame member is not exposed, and the outer surface of the tire can be protected and the weather resistance can be improved while maintaining the design freedom of the tire frame member itself.

  Moreover, in the tire of Claim 1, it has a decoration part on the surface of a coating layer. Since the coating layer is made of a resin material, even when the resin material contains an anti-aging agent, the resin itself can be colored as compared with the rubber tire, and can correspond to various colors. Therefore, discoloration and deterioration of the decoration part are suppressed, and the hue hardly changes, so that the appearance of the decoration part can be maintained. Furthermore, when providing a decoration part in a tire, since it is not necessary to provide a color rubber and a barrier layer, the weight increase of a tire and a production process can be suppressed.

Here, in the present invention, the “resin material” refers to a material that contains at least a resin and may further contain a component other than a resin. When the resin material does not contain a component other than a resin, the resin material is only a resin. Consists of.
Further, in this specification, “resin” is a concept including thermoplastic resin, thermosetting resin, so-called engineering plastic, but does not include natural rubber. Further, the thermoplastic resin includes a thermoplastic elastomer.
Further, the “elastomer” is a copolymer having a crystalline hard segment having a high melting point or a hard segment having a high cohesive force and an amorphous polymer having a soft segment having a low glass transition temperature. Is a resin.

  The tire according to claim 2 includes at least a transparent protective layer laminated on the decorative portion.

  According to the tire according to claim 2, the decoration part is covered with at least a transparent protective layer, thereby suppressing discoloration and loss of the decoration part and maintaining the appearance of the decoration part for a long time. Excellent temporal stability of the appearance of the decorative part. In addition, "transparent" represents a state where the decorative portion covered with the protective layer is visible, and more specifically, means that the light (visible light) transmittance is 70% or more.

  According to the first aspect of the invention, while maintaining the freedom of design of the tire frame member itself, the weather resistance of the outer surface of the tire is improved, the weight of the tire is suppressed, and the appearance of the decoration portion is maintained. A compatible tire can be provided.

  According to the invention which concerns on Claim 2, the tire excellent in the temporal stability of the external appearance of a decoration part can be provided further.

(A) is sectional drawing of the pneumatic tire which concerns on this embodiment, (B) is a partial expansion perspective sectional view when the pneumatic tire which concerns on this embodiment is mounted | worn to a rim | limb. It is a partial expanded sectional view of the tire shoulder part of Drawing 1 (A). It is a partial cross section figure of the state by which the metal mold | die used by this embodiment was open | released. It is a partial cross section figure of the state where the metal mold used by this embodiment was closed. It is sectional drawing of the tire frame member and tread part before the tread part of the pneumatic tire which concerns on this embodiment is adhere | attached. It is sectional drawing of the pneumatic tire which concerns on other embodiment of this invention.

  The tire of the present invention is made of a resin material, and includes a tire frame member having at least a tread portion and a bead portion, and a resin material. The tire is formed on the outer side of the tire frame member from the bead portion to the tread portion, and is added to the surface. And a coating layer having a decorative portion. The tire preferably includes a transparent protective layer at least on the decorative portion.

[Tire frame members]
The tire frame member is made of a resin material and has at least a tread portion and a bead portion.
A configuration example of the tire frame member will be described with reference to FIG.
As shown in FIG. 1 (A), the tire according to the present embodiment is a pneumatic tire that is used while being filled with air. The tire 10 includes an annular tire frame member 17. The tire frame member 17 includes a pair of bead portions 12, a side portion 14 that extends outward from the bead portion 12 in the tire radial direction, and a crown portion 16 that connects the tire radial direction outer ends of each side portion 14. I have.

(Coating layer)
The coating layer is made of a resin material, is formed on the outer side of the tire frame member from the bead portion to the tread portion, and has a decorative portion on the surface.
A configuration example of the coating layer will be described with reference to FIG.
As shown in FIG. 1A, a coating layer 24 is formed on the tire frame member 17 from the bead portion 12 to the tread portion 30.
Moreover, the surface of the coating layer 24 has a decoration part. Here, the surface of the coating layer 24 is a surface on the side visually recognized from the outside of the tire 10, and is a surface on the side opposite to the side portion 14 side of the coating layer 24.

The decoration part is a mark that shows the name of the manufacturer of the tire, the brand name of the tire, the size of the tire, the date of manufacture, etc. with letters, symbols, pictures, figures, etc., decorations formed by patterns, colors, etc. Composed.
The decorating portion can be provided by applying a known ink to the coating layer 24, or by bonding or printing a film provided with a mark or decoration on the coating layer 24. Moreover, you may transfer the mark etc. which were formed on the film to the coating layer 24 by thermal transfer using a transfer film.
Examples of the method for applying the ink to the coating layer 24 include a blade coating method, a Mayer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method. Alternatively, the decoration portion may be formed by ejecting ink droplets onto the coating layer 24 by an inkjet method.
Furthermore, the ink can be prepared by mixing a known colorant such as a pigment or a dye with a solvent and, if necessary, a pigment dispersant, and may be a liquid ink having a low viscosity. High paste-like ink may be used.

In addition, the formation of the decorative portion on the surface of the coating layer 24 may be performed during tire manufacture or after completion of the tire.
Next, the resin material constituting the tire frame member and the coating layer will be described.

[Resin material]
Resin materials are used for the tire frame member and the covering layer, and different resin materials may be used, or the same resin material may be used. Further, the resin material used for the tire frame member and the coating layer may be one type or two or more types, and resin materials having different physical properties such as elastic modulus can be used depending on the use of the tire.
In the present invention, when simply referred to as “elastic modulus”, it means “tensile elastic modulus defined in JIS K7113: 1995”.

  In the present invention, the “resin material” includes at least a resin (resin component) and may include other components such as an additive. When the resin material does not contain any component other than the resin component, the resin material is composed only of resin.

Further, in this specification, “resin” is a concept including a thermoplastic resin and a thermosetting resin, but does not include natural rubber. Further, the thermoplastic resin includes a thermoplastic elastomer.
Here, the “elastomer” is a copolymer having a crystalline polymer having a high melting point or a hard cohesive polymer and an amorphous polymer having a low glass transition temperature. The resin consisting of

〔resin〕
Examples of the resin include thermoplastic resins (including thermoplastic elastomers) and thermosetting resins. The resin material may be, for example, a thermoplastic elastomer described later alone, or a combination of a plurality of these, or a combination of a thermoplastic elastomer and a thermoplastic resin that is not an elastomer. Also good.

  The resin material constituting the tire frame member is preferably a thermoplastic resin, and more preferably a thermoplastic elastomer. Hereinafter, the resin used for the resin material for forming the tire frame member and the covering layer will be described focusing on the thermoplastic resin.

-Thermoplastic resin (including thermoplastic elastomer)-
A thermoplastic resin (including a thermoplastic elastomer) refers to a high molecular compound that softens and flows as the temperature rises and becomes relatively hard and strong when cooled.
In the present specification, among these thermoplastic resins, the material softens and flows as the temperature rises, becomes a relatively hard and strong state when cooled, and the polymer compound having rubber-like elasticity is heated. A plastic elastomer is used. On the other hand, among the thermoplastic resins, the material softens and flows as the temperature rises, and when cooled, the material becomes relatively hard and strong. As a distinction.

  Thermoplastic resins (including thermoplastic elastomers) include polyolefin-based thermoplastic elastomers (TPO), polystyrene-based thermoplastic elastomers (TPS), polyamide-based thermoplastic elastomers (TPA), polyurethane-based thermoplastic elastomers (TPU), and polyesters. Thermoplastic elastomer (TPC) and dynamically cross-linked thermoplastic elastomer (TPV), and non-elastomer polyolefin thermoplastic resin, non-elastomer polystyrene thermoplastic resin, non-elastomer polyamide thermoplastic resin, and elastomer Non-polyester thermoplastic resin etc. are mentioned. The thermoplastic resin contained in the resin material is preferably at least one selected from polyester-based thermoplastic elastomers and polyamide-based thermoplastic elastomers.

(Polyester thermoplastic elastomer)
Polyester-based thermoplastic elastomers consist of hard segments with at least a crystalline polyester and a high melting point, and soft segments with other polymers (such as polyester or polyether) that are amorphous and have a low glass transition temperature. Material.
The polyester-based thermoplastic elastomer may be referred to as “TPC” (Thermo Plastic Polymer Elastomer).

An aromatic polyester can be used as the polyester that forms the hard segment. The aromatic polyester can be formed, for example, from an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol. The aromatic polyester is preferably polybutylene terephthalate derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol, and further, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, Dicarboxylic acid components such as naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or ester-forming derivatives thereof, and diols having a molecular weight of 300 or less For example, aliphatic diols such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, 1,4-cyclohexanedimethanol, tricyclodecane dimethylo Alicyclic diols such as alcohol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [ 4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4′-dihydroxy-p-terphenyl, 4,4′-dihydroxy-p- It may be a polyester derived from an aromatic diol such as quarterphenyl, or a copolyester in which two or more of these dicarboxylic acid components and diol components are used in combination. It is also possible to copolymerize a trifunctional or higher polyfunctional carboxylic acid component, polyfunctional oxyacid component, polyfunctional hydroxy component, and the like in a range of 5 mol% or less.
Examples of the polyester that forms the hard segment include polyethylene terephthalate, prebutylene terephthalate, polymethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, and polybutylene terephthalate is preferable.

Examples of the polymer forming the soft segment include aliphatic polyesters and aliphatic polyethers.
Examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, and poly (propylene oxide). And ethylene oxide addition polymer of glycol, and a copolymer of ethylene oxide and tetrahydrofuran.
Examples of the aliphatic polyester include poly (ε-caprolactone), polyenantlactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate.
Of these aliphatic polyethers and aliphatic polyesters, poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol ethylene oxide adduct, poly (ε -Caprolactone), polybutylene adipate, polyethylene adipate and the like are preferred.

  Moreover, as a number average molecular weight of the polymer which comprises the said soft segment, 300-6000 are preferable from a viewpoint of toughness and low temperature flexibility. Furthermore, the mass ratio (x: y) to the hard segment (x) and the soft segment (y) is preferably 99: 1 to 20:80, more preferably 98: 2 to 30:70, from the viewpoint of moldability. preferable.

  As a combination of the above-mentioned hard segment and a soft segment, each combination of a hard segment and a soft segment mentioned above can be mentioned. Among these, a combination of polybutylene terephthalate and soft segment aliphatic polyether is preferable for the hard segment, polybutylene terephthalate for the hard segment, and poly (ethylene oxide) glycol for the soft segment is more preferable.

  Examples of the polyester-based thermoplastic elastomer include, for example, commercially available “Hytrel” series (for example, 3046, 5557, 6347, 4047, 4767, 7247, etc.) manufactured by Toray DuPont, and “Perprene” series (P30B, manufactured by Toyobo Co., Ltd.). P40B, P40H, P55B, P70B, P150B, P280B, P450B, P150M, S1001, S2001, S5001, S6001, S9001, etc.) can be used.

(Polyamide thermoplastic elastomer)
In the present invention, the “polyamide thermoplastic elastomer” is a copolymer having a crystalline polymer having a high melting point and a non-crystalline polymer having a low glass transition temperature. It means a thermoplastic resin material having an amide bond (—CONH—) in the main chain of the polymer constituting the hard segment.
The polyamide-based thermoplastic elastomer may be simply referred to as “TPA” (Thermoplastic Amid elastomer).

  The polyamide-based thermoplastic elastomer comprises at least a hard segment having a crystalline and high melting point, and other polymers (for example, polyester or polyether) are non-crystalline and have a soft segment having a low glass transition temperature. Materials. The polyamide thermoplastic elastomer may use a chain extender such as dicarboxylic acid in addition to the hard segment and the soft segment. Examples of the polyamide forming the hard segment include polyamides produced by monomers represented by the following general formula (1) or general formula (2).

In general formula (1), R ¹ represents a molecular chain of a hydrocarbon having 2 to 20 carbon atoms or an alkylene group having 2 to 20 carbon atoms.

In General Formula (2), R ² represents a molecular chain of a hydrocarbon having 3 to 20 carbon atoms or an alkylene group having 3 to 20 carbon atoms.

In general formula (1), R ¹ is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms or an alkylene group having 3 to 18 carbon atoms, and a hydrocarbon molecular chain having 4 to 15 carbon atoms or 4 carbon atoms. To 15 alkylene groups are more preferable, and hydrocarbon chains having 10 to 15 carbon atoms or alkylene groups having 10 to 15 carbon atoms are particularly preferable. In general formula (2), R ² is preferably a hydrocarbon molecular chain having 3 to 18 carbon atoms or an alkylene group having 3 to 18 carbon atoms, and a molecular chain or carbon having 4 to 15 carbon atoms. An alkylene group having 4 to 15 carbon atoms is more preferable, and a molecular chain of a hydrocarbon having 10 to 15 carbon atoms or an alkylene group having 10 to 15 carbon atoms is particularly preferable.
Examples of the monomer represented by the general formula (1) or the general formula (2) include ω-aminocarboxylic acid and lactam. Examples of the polyamide forming the hard segment include polycondensates of these ω-aminocarboxylic acids and lactams, and co-condensation polymers of diamines and dicarboxylic acids.

Examples of the ω-aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. And aliphatic ω-aminocarboxylic acid. Moreover, as a lactam, C5-C20 aliphatic lactams, such as lauryl lactam, (epsilon) -caprolactam, udecan lactam, (omega) -enantolactam, 2-pyrrolidone, etc. can be mentioned.
Examples of the diamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2, Examples thereof include diamine compounds such as aliphatic diamines having 2 to 20 carbon atoms such as 4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 3-methylpentamethylenediamine, and metaxylenediamine. Further, dicarboxylic ^{acids, HOOC- (R 3) m-} COOH (R 3: the molecular chain of a hydrocarbon of 3 to 20 carbon atoms, m: 0 or 1) can be represented by, for example, oxalic acid, succinic acid And aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid.
As the polyamide that forms the hard segment, a polyamide obtained by ring-opening polycondensation of lauryl lactam, ε-caprolactam, or udecan lactam can be preferably used.

Examples of the polymer that forms the soft segment include polyesters and polyethers, such as polyethylene glycol, propylene glycol, polytetramethylene ether glycol, ABA type triblock polyether, and the like. A single compound or two or more compounds can be used. Moreover, polyether diamine etc. which are obtained by making animonia etc. react with the terminal of polyether can be used.
Here, the “ABA type triblock polyether” means a polyether represented by the following general formula (3).

  In general formula (3), x and z represent the integer of 1-20. y represents an integer of 4 to 50.

  In the general formula (3), each of x and z is preferably an integer of 1 to 18, more preferably an integer of 1 to 16, particularly preferably an integer of 1 to 14, and most preferably an integer of 1 to 12. . In the general formula (3), each of y is preferably an integer of 5 to 45, more preferably an integer of 6 to 40, particularly preferably an integer of 7 to 35, and most preferably an integer of 8 to 30. .

  Examples of the combination of the hard segment and the soft segment include the combinations of the hard segment and the soft segment mentioned above. Among these, lauryl lactam ring-opening polycondensate / polyethylene glycol combination, lauryl lactam ring-opening polycondensate / polypropylene glycol combination, lauryl lactam ring-opening polycondensate / polytetramethylene ether glycol combination, lauryl lactam The ring-opening polycondensate / ABA triblock polyether combination is preferred, and the lauryl lactam ring-opening polycondensate / ABA triblock polyether combination is particularly preferred.

  The number average molecular weight of the polymer (polyamide) constituting the hard segment is preferably 300 to 30000 from the viewpoint of melt moldability. Moreover, as a number average molecular weight of the polymer which comprises the said soft segment, 200-20000 are preferable from a viewpoint of toughness and low temperature flexibility. Further, the mass ratio (x: y) to the hard segment (x) and the soft segment (y) is preferably 50:50 to 90:10, more preferably 50:50 to 80:20, from the viewpoint of moldability. preferable.

  The polyamide-based thermoplastic elastomer can be synthesized by copolymerizing the polymer forming the hard segment and the polymer forming the soft segment by a known method.

  Examples of the polyamide-based thermoplastic elastomer include, for example, a commercially available “UBESTA XPA” series (for example, XPA9063X1, XPA9055X1, XPA9048X2, XPA9048X1, XPA9040X1, XPA9040X2XPA9044, etc.) of Daicel Eponic Corporation. “Vestamide” series (for example, E40-S3, E47-S1, E47-S3, E55-S1, E55-S3, E55-S4, E55-K1W2, EX9200, E50-R2) and the like can be used.

(Polyolefin thermoplastic elastomer)
“Polyolefin thermoplastic elastomer” means a hard segment having at least a polyolefin having a crystalline and high melting point, and other polymers (for example, the above-mentioned polyolefin or other polyolefin) being amorphous and having a low glass transition temperature. The material which comprises is mentioned. Examples of the polyolefin forming the hard segment include polyethylene, polypropylene, isotactic polypropylene, polybutene, and the like.
The polyolefin-based thermoplastic elastomer may be simply referred to as “TPO” (Thermo Plastic Olefin elastomer).

  The polyolefin-based thermoplastic elastomer is not particularly limited. However, a crystalline polyolefin constitutes a hard segment having a high melting point, and an amorphous polymer constitutes a soft segment having a low glass transition temperature. A polymer is mentioned.

  Examples of the polyolefin-based thermoplastic elastomer include olefin-α-olefin random copolymers, olefin block copolymers, and the like. For example, propylene block copolymers, ethylene-propylene copolymers, propylene-1-hexene copolymers. Polymer, propylene-4-methyl-1-pentene copolymer, propylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-pentene copolymer, ethylene-1-butene copolymer Polymer, 1-butene-1-hexene copolymer, 1-butene-4-methyl-pentene, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, Ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, Lene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer, propylene-methyl methacrylate copolymer, propylene-ethyl methacrylate copolymer, propylene-butyl methacrylate copolymer , Propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, propylene-vinyl acetate copolymer, and the like.

Examples of the polyolefin-based thermoplastic elastomer include a propylene block copolymer, an ethylene-propylene copolymer, a propylene-1-hexene copolymer, a propylene-4-methyl-1-pentene copolymer, and a propylene-1-butene copolymer. Polymer, ethylene-1-hexene copolymer, ethylene-4-methyl-pentene copolymer, ethylene-1-butene copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene- Ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, propylene-methacrylic acid copolymer, propylene- Methyl methacrylate copolymer, propylene Ethyl tacrylate copolymer, propylene-butyl methacrylate copolymer, propylene-methyl acrylate copolymer, propylene-ethyl acrylate copolymer, propylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, propylene- Vinyl acetate copolymers are preferred, ethylene-propylene copolymers, propylene-1-butene copolymers, ethylene-1-butene copolymers, ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, More preferred are ethylene-ethyl acrylate copolymers and ethylene-butyl acrylate copolymers.
Moreover, you may use combining 2 or more types of polyolefin resin like ethylene and propylene. The polyolefin content in the polyolefin-based thermoplastic elastomer is preferably 50% by mass or more and 100% by mass or less.

  The number average molecular weight of the polyolefin-based thermoplastic elastomer is preferably 5,000 to 10,000,000. When the number average molecular weight of the polyolefin-based thermoplastic elastomer is in the range of 5,000 to 10,000,000, the mechanical properties of the resin material are sufficient and the processability is also excellent. From the same viewpoint, it is more preferably 7,000 to 1,000,000, and particularly preferably 10,000 to 1,000,000. Thereby, the mechanical properties and processability of the resin material can be further improved. Moreover, as a number average molecular weight of the polymer which comprises the said soft segment, 200-6000 are preferable from a viewpoint of toughness and low temperature flexibility. Furthermore, the mass ratio (x: y) of the hard segment (x) and the soft segment (y) is preferably 50:50 to 95: 5, and more preferably 50:50 to 90:10, from the viewpoint of moldability. .

  The polyolefin-based thermoplastic elastomer can be synthesized by copolymerizing the polymer that forms the hard segment and the polymer that forms the soft segment by a known method.

Moreover, as the polyolefin thermoplastic elastomer, one obtained by acid-modifying a thermoplastic elastomer may be used.
The above “obtained by acid-modifying a polyolefin thermoplastic elastomer” means that an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group, or a phosphoric acid group is bonded to the polyolefin thermoplastic elastomer. For example, when an unsaturated carboxylic acid (generally maleic anhydride) is used as the unsaturated compound having an acidic group, an unsaturated bond site of the unsaturated carboxylic acid is bonded to the olefin-based thermoplastic elastomer (for example, Graft polymerization).

  The compound having an acidic group is preferably a compound having a carboxylic acid group which is a weak acid group from the viewpoint of suppressing deterioration of the polyolefin thermoplastic elastomer, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid. An acid etc. are mentioned.

Examples of the polyolefin-based thermoplastic elastomer as described above include, for example, commercially available “Tuffmer” series manufactured by Mitsui Chemicals (for example, A0550S, A1050S, A4050S, A1070S, A4070S, A35070S, A1085S, A4085S, A7090, A70090, MH7007). MH7010, XM-7070, XM-7080, BL4000, BL2481, BL3110, BL3450, P-0275, P-0375, P-0775, P-0180, P-0280, P-0480, P-0680), Mitsui DuPont Polychemical Co., Ltd. “Nuclele” series (for example, AN4214C, AN4225C, AN42115C, N0903HC, N0908C, AN42012C, N410, N1050H, N11 8C, N1110H, N1207C, N1214, AN4221C, N1525, N1560, N0200H, AN4228C, AN4213C, N035C, “Elvalloy AC” series (eg, 1125AC, 1209AC, 1218AC, 1609AC, 1820AC, 1913AC, 2112AC, 2116AC, 2615AC, 2715 3117AC, 3427AC, 3717AC), Sumitomo Chemical Co., Ltd. “Aclift” series, “Evertate” series, Tosoh Corporation “Ultrasen” series, and the like.
Further, as the polyolefin-based thermoplastic elastomer, for example, “Prime TPO” series (for example, E-2900H, F-3900H, E-2900, F-3900, J-5900, E-manufactured by a commercially available prime polymer) 2910, F-3910, J-5910, E-2710, F-3710, J-5910, E-2740, F-3740, R110MP, R110E, T310E, M142E, etc.) can also be used.

(Polystyrene thermoplastic elastomer)
In the polystyrene-based thermoplastic elastomer, at least polystyrene constitutes a hard segment, and other polymers (eg, polybutadiene, polyisoprene, polyethylene, hydrogenated polybutadiene, hydrogenated polyisoprene, etc.) constitute a soft segment having a low glass transition temperature. Materials. Further, as the polystyrene-based thermoplastic elastomer, synthetic rubber such as vulcanized SBR resin may be used.
The polystyrene-based thermoplastic elastomer may also be referred to as “TPS” (Thermoplastic Stylene elastomer).

  As the polystyrene-based thermoplastic elastomer, either an acid-modified polystyrene-based thermoplastic elastomer modified with an acid group or an unmodified polystyrene-based thermoplastic elastomer can be used.

  As the polystyrene forming the hard segment, for example, those obtained by a known radical polymerization method or ionic polymerization method can be suitably used, and examples thereof include polystyrene having anion living polymerization. Examples of the polymer forming the soft segment include polybutadiene, polyisoprene, poly (2,3-dimethyl-butadiene), and the like. The acid-modified polystyrene-based thermoplastic elastomer can be obtained by acid-modifying an unmodified polystyrene-based thermoplastic elastomer as described later.

  As a combination of the above-mentioned hard segment and a soft segment, each combination of a hard segment and a soft segment mentioned above can be mentioned. Among these, a combination of polystyrene / polybutadiene and a combination of polystyrene / polyisoprene are preferable. Moreover, in order to suppress the unintended cross-linking reaction of the thermoplastic elastomer, the soft segment is preferably hydrogenated.

The number average molecular weight of the polymer (polystyrene) constituting the hard segment is preferably 5,000 to 500,000, and preferably 10,000 to 200,000.
Moreover, as a number average molecular weight of the polymer which comprises the said soft segment, 5000-1 million are preferable, 10000-800000 are more preferable, and 30000-500000 are especially preferable. Furthermore, the volume ratio (x: y) to the hard segment (x) and the soft segment (y) is preferably 5:95 to 80:20, more preferably 10:90 to 70:30, from the viewpoint of moldability. preferable.

The polystyrene-based thermoplastic elastomer can be synthesized by copolymerizing the polymer that forms the hard segment and the polymer that forms the soft segment by a known method.
Examples of the polystyrene-based thermoplastic elastomer include styrene-butadiene copolymer [SBS (polystyrene-poly (butylene) block-polystyrene), SEBS (polystyrene-poly (ethylene / butylene) block-polystyrene)], styrene-isoprene copolymer. Polymer [polystyrene-polyisoprene block-polystyrene), styrene-propylene copolymer [SEP (polystyrene- (ethylene / propylene) block), SEPS (polystyrene-poly (ethylene / propylene) block-polystyrene), SEEPS (polystyrene) -Poly (ethylene-ethylene / propylene) block-polystyrene), SEB (polystyrene (ethylene / butylene) block) and the like are mentioned, and SEBS is particularly preferable.

  Examples of the unmodified polystyrene-based thermoplastic elastomer include “Tough Tech” series manufactured by Asahi Kasei Corporation (for example, H1031, H1041, H1043, H1051, H1052, H1053, H1062, H1082, H1141, H1221, H1272), SEBS ("Hibler" 5127, 5125, etc.) manufactured by Kuraray Co., Ltd., SEPS ("Septon" 2002, 2063, S2004, S2006, etc.) and the like can be used.

-Acid-modified polystyrene-based thermoplastic elastomer-
“Acid-modified polystyrene-based thermoplastic elastomer” is an unmodified polystyrene-based thermoplastic elastomer that is acid-modified by bonding an unsaturated compound having an acidic group such as a carboxylic acid group, a sulfuric acid group, or a phosphoric acid group. It means a plastic elastomer. The acid-modified polystyrene-based thermoplastic elastomer can be obtained, for example, by bonding (for example, graft polymerization) an unsaturated bond site of unsaturated carboxylic acid or unsaturated carboxylic acid anhydride to the polystyrene-based thermoplastic elastomer.

  As the (unsaturated) compound having an acidic group, a compound having a carboxylic acid group which is a weak acid group is preferable from the viewpoint of suppressing deterioration of the polyamide-based thermoplastic elastomer. For example, acrylic acid, methacrylic acid, itaconic acid, croton Examples include acids, isocrotonic acid, maleic acid and the like.

  Examples of the acid-modified polystyrene-based thermoplastic elastomer include Asahi Kasei Corporation, Tuftec, for example, M1943, M1911, M1913, Kraton, FG19181G, and the like.

The acid value of the acid-modified polystyrene thermoplastic _{elastomers, 0mg (CH 3 ONa) /} g , greater 20mg _(CH 3 ONa) / g is preferably less _{that, 0mg (CH 3 ONa) /} g and beyond 17 mg (CH ₃ ONa) / g or less, more preferably 0 mg (CH ₃ ONa) / g and particularly preferably 15 mg (CH ₃ ONa) / g or less.

(Polyurethane thermoplastic elastomer)
Polyurethane-based thermoplastic elastomers consist of hard segments in which at least polyurethane forms pseudo-crosslinks due to physical aggregation, and other polymers are amorphous and have soft segments with low glass transition temperatures. Can be mentioned.
The polyurethane-based thermoplastic elastomer may be simply referred to as “TPU” (ThermoPlastic Urethan elastomer).

  Specifically, the polyurethane-based thermoplastic elastomer includes, for example, a soft segment including a unit structure represented by the following structural unit (U-1) and a unit structure represented by the following structural unit (U-2). It can represent as a copolymer containing the hard segment to contain.

  In the structural unit (U-1) and the structural unit (U-2), P represents a long-chain aliphatic polyether or a long-chain aliphatic polyester. R represents an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon. P ′ represents a short chain aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon.

In the structural unit (U-1), as the long-chain aliphatic polyether and long-chain aliphatic polyester represented by P, for example, those having a molecular weight of 500 to 5000 can be used. The P is derived from a diol compound containing a long-chain aliphatic polyether represented by the P and a long-chain aliphatic polyester. Such diol compounds include, for example, polyethylene glycol, propylene glycol, polytetramethylene ether glycol, poly (butylene adipate) diol, poly-ε-caprolactone diol, poly (hexamethylene) having a molecular weight within the above range. Carbonate) diol, the ABA triblock polyether [polyether represented by the general formula (3)] and the like.
These may be used alone or in combination of two or more.

In the structural unit (U-1) and the structural unit (U-2), R is derived from a diisocyanate compound containing an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon represented by the R. . Examples of the aliphatic diisocyanate compound containing the aliphatic hydrocarbon represented by R include 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate, and 1,6-hexamethylene diisocyanate. Etc.
Examples of the diisocyanate compound containing the alicyclic hydrocarbon represented by R include 1,4-cyclohexane diisocyanate and 4,4-cyclohexane diisocyanate. Furthermore, examples of the aromatic diisocyanate compound containing the aromatic hydrocarbon represented by R include 4,4′-diphenylmethane diisocyanate and tolylene diisocyanate.
These may be used alone or in combination of two or more.

In the structural unit (U-2), as the short-chain aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon represented by P ′, for example, those having a molecular weight of less than 500 may be used. it can. The P ′ is derived from a diol compound containing a short chain aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon represented by the P ′. Examples of the aliphatic diol compound containing the short-chain aliphatic hydrocarbon represented by P ′ include glycol and polyalkylene glycol, such as ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, Examples include 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol and 1,10-decanediol. It is done.
Examples of the alicyclic diol compound containing the alicyclic hydrocarbon represented by P ′ include cyclopentane-1,2-diol, cyclohexane-1,2-diol, and cyclohexane-1,3-diol. , Cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol and the like.
Furthermore, examples of the aromatic diol compound containing an aromatic hydrocarbon represented by P ′ include hydroquinone, resorcin, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4 ′. -Dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, bisphenol A, 1 , 1-di (4-hydroxyphenyl) cyclohexane, 1,2-bis (4-hydroxyphenoxy) ethane, 1,4-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. .
These may be used alone or in combination of two or more.

The number average molecular weight of the polymer (polyurethane) constituting the hard segment is preferably 300 to 1500 from the viewpoint of melt moldability. Further, the number average molecular weight of the polymer constituting the soft segment is preferably 500 to 20000, more preferably 500 to 5000, and particularly preferably 500 to 5000, from the viewpoints of flexibility and thermal stability of the polyurethane-based thermoplastic elastomer. 3000. The mass ratio (x: y) to the hard segment (x) and the soft segment (y) is preferably 15:85 to 90:10, more preferably 30:70 to 90:10, from the viewpoint of moldability. preferable.
The polyurethane-based thermoplastic elastomer can be synthesized by copolymerizing the polymer that forms the hard segment and the polymer that forms the soft segment by a known method. As the polyurethane-based thermoplastic elastomer, for example, thermoplastic polyurethane described in JP-A-5-331256 can be used.
As the polyurethane-based thermoplastic elastomer, specifically, a combination of a hard segment composed of an aromatic diol and an aromatic diisocyanate and a soft segment composed of a polycarbonate is preferable. Tolylene diisocyanate (TDI) / polyester-based polyol Polymer, TDI / polyether polyol copolymer, TDI / caprolactone polyol copolymer, TDI / polycarbonate polyol copolymer, 4,4′-diphenylmethane diisocyanate (MDI) / polyester polyol copolymer, MDI / Polyether-based polyol copolymer, MDI / caprolactone-based polyol copolymer, MDI / polycarbonate-based polyol copolymer, MDI + hydroquinone / polyhexamethylene carbonate copolymer TDI / polyester polyol copolymer, TDI / polyether polyol copolymer, MDI / polyester polyol copolymer, MDI / polyether polyol copolymer, MDI + hydroquinone / polyhexamethylene carbonate copolymer Is more preferable.

  Examples of the polyurethane-based thermoplastic elastomer include, for example, commercially available “Elastollan” series (for example, ET680, ET880, ET690, ET890, etc.) manufactured by BASF, and “Clamiron U” series (manufactured by Kuraray Co., Ltd.). For example, 2000 series, 3000 series, 8000 series, 9000 series, “Milactolan” series (for example, XN-2001, XN-2004, P390RSUP, P480RSUI, P26MRNAT, E490, E590, P890) manufactured by Japan Miraclan Co., Ltd. Can be used.

  The above-mentioned thermoplastic elastomer can be synthesized by copolymerizing the polymer forming the hard segment and the polymer forming the soft segment by a known method.

  Next, various thermoplastic resins that are not elastomers will be described.

(Polyolefin thermoplastic resin that is not an elastomer)
The polyolefin-based resin that is not an elastomer is a polyolefin-based resin having a higher elastic modulus than the polyolefin-based thermoplastic elastomer described above.
Examples of polyolefin-based thermoplastic resins that are not elastomers include homopolymers, random copolymers, block copolymers, and the like of α-olefins such as propylene and ethylene, and cyclic olefins such as cycloolefin. Specific examples include polyethylene-based thermoplastic resins, polypropylene-based thermoplastic resins, polybutadiene-based thermoplastic resins, and polypropylene-based thermoplastic resins are particularly preferable from the viewpoint of heat resistance and processability.
Specific examples of the polypropylene-based thermoplastic resin that is not an elastomer include a propylene homopolymer, a propylene-α-olefin random copolymer, a propylene-α-olefin block copolymer, and the like. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, Examples include α-olefins having about 3 to 20 carbon atoms such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene.

  The polyolefin-based thermoplastic resin may be a chlorinated polyolefin-based resin in which some or all of the hydrogen atoms in the molecule are replaced with chlorine atoms. Examples of the chlorinated polyolefin resin include chlorinated polyethylene resins.

(Polystyrene thermoplastic resin that is not an elastomer)
The polystyrene-based thermoplastic resin that is not an elastomer is a polystyrene-based thermoplastic resin having a higher elastic modulus than the polystyrene-based thermoplastic elastomer described above.
As the polystyrene-based thermoplastic resin, for example, those obtained by a known radical polymerization method or ionic polymerization method can be suitably used, and examples thereof include polystyrene having anion living polymerization. Examples of the polystyrene-based thermoplastic resin include a polymer containing a styrene molecular skeleton and a copolymer of styrene and acrylonitrile.
Among these, an acrylonitrile / butadiene / styrene copolymer and a hydrogenated product thereof; a blend of acrylonitrile / styrene copolymer and polybutadiene or a hydrogenated product thereof are preferable. Specific examples of the polystyrene-based thermoplastic resin include polystyrene (so-called PS resin), acrylonitrile / styrene resin (so-called AS resin), acrylic-styrene-acrylonitrile resin (so-called ASA resin), and acrylonitrile / butadiene / styrene resin (so-called so-called AS resin). Examples thereof include ABS resins (including blends and copolymers), hydrogenated ABS resins (so-called AES resins), acrylonitrile-chlorinated polyethylene-styrene copolymers (so-called ACS resins), and the like.

  As described above, the AS resin is an acrylonitrile / styrene resin, which is a copolymer having styrene and acrylonitrile as main components, but is an aromatic vinyl compound such as α-methylstyrene, vinyltoluene, divinylbenzene, or cimethacrylonitrile. (Meth) acrylic acid alkyl esters such as methyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, stearyl acrylate, maleimide, N- Maleimide monomers such as methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, vinyl alkyls Or the like may be further copolymerized ether.

  Further, as the AS resin, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or those obtained by graft polymerization or copolymerization of epoxy group-containing vinyl monomers are preferable, and unsaturated acid anhydrides or More preferred is a graft polymerized or copolymerized epoxy group-containing vinyl monomer.

  Such epoxy group-containing vinyl monomers are compounds that share both radically polymerizable vinyl groups and epoxy groups in one molecule. Specific examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and itacon. Examples thereof include glycidyl esters of unsaturated organic acids such as glycidyl acid, glycidyl ethers such as allyl glycidyl ether, and the aforementioned derivatives such as 2-methylglycidyl methacrylate, among which glycidyl acrylate and glycidyl methacrylate can be preferably used. . Moreover, these can be used individually or in combination of 2 or more types.

  Unsaturated acid anhydrides are compounds that share both radically polymerizable vinyl groups and acid anhydrides in one molecule, and preferred examples include maleic anhydride.

  The ASA resin is composed of an acrylate monomer, a styrene monomer, and an acrylonitrile monomer, and has rubbery properties and thermoplasticity.

  As the ABS resin, for example, a resin obtained by graft-polymerizing acrylonitrile-styrene resin with olefin rubber (for example, polybutadiene rubber) to about 40% by mass or less can be given. Examples of the AES resin include a resin obtained by graft polymerization of acrylonitrile-styrene resin with ethylene-propylene copolymer rubber (for example, EP rubber) to about 40% by mass or less.

(Non-elastomer thermoplastic resin)
The polyamide-based resin that is not an elastomer is a polyamide-based resin having a higher elastic modulus than the polyamide-based thermoplastic elastomer described above.
Examples of the polyamide-based thermoplastic resin include polyamides that constitute the hard segment of the above-described polyamide-based thermoplastic elastomer. Examples of the polyamide-based thermoplastic resin include polyamide (amide 6) obtained by ring-opening polycondensation of ε-caprolactam, polyamide (amide 11) obtained by ring-opening polycondensation of undecane lactam, and polyamide (amide 11) obtained by ring-opening polycondensation of lauryl lactam ( Examples thereof include amide 12), polycondensation polyamide (amide 66) of diamine and dibasic acid, and polyamide (amide MX) having metaxylenediamine as a structural unit.

The amide 6 can be represented by, for example, {CO— (CH ₂ ) ₅ —NH} _n (n represents the number of repeating units).
The amide 11 can be represented by, for example, {CO— (CH ₂ ) ₁₀ —NH} _n (n represents the number of repeating units).
The amide 12 can be represented by, for example, {CO— (CH ₂ ) ₁₁ —NH} _n (n represents the number of repeating units).
The amide 66 can be represented by, for example, {CO (CH ₂ ) ₄ CONH (CH ₂ ) ₆ NH} _n (n represents the number of repeating units).

  The amide MX having meta-xylenediamine as a structural unit can be represented by, for example, the following structural unit (A-1) [n represents the number of repeating units in (A-1)].

  The polyamide-based thermoplastic resin may be a homopolymer composed only of the structural unit, or may be a copolymer of the structural unit (A-1) and another monomer. In the case of a copolymer, in each polyamide-based thermoplastic resin, the content of the structural unit (A-1) is preferably 60% by mass or more.

  As a number average molecular weight of a polyamide-type thermoplastic resin, 300-30000 are preferable. Moreover, as a number average molecular weight of the polymer which comprises the said soft segment, 200-20000 are preferable from a viewpoint of toughness and low temperature flexibility.

A commercially available product may be used as the polyamide-based resin that is not an elastomer.
As the amide 6, for example, “UBE nylon” 1022B, 1011FB manufactured by Ube Industries, Ltd. and the like can be used.
As the amide 12, “UBE nylon” manufactured by Ube Industries, for example, 3024U can be used. As the amide 66, “UBE nylon” or the like can be used. In addition, as the amide MX, for example, commercially available MX nylon (S6001, S6021, S6011) manufactured by Mitsubishi Gas Chemical Co., Inc. can be used.

(Non-elastomer thermoplastic resin)
A polyester-based resin that is not an elastomer is a resin having a higher elastic modulus than the polyester-based thermoplastic elastomer described above and having an ester bond in the main chain.
Although it does not specifically limit as a polyester-type thermoplastic resin, It is preferable that it is the same kind of resin as the polyester-type thermoplastic resin which the hard segment in the above-mentioned polyester-type thermoplastic elastomer contains. The polyester resin that is not an elastomer may be crystalline or amorphous, and examples thereof include aliphatic polyesters and aromatic polyesters. The aliphatic polyester may be a saturated aliphatic polyester or an unsaturated aliphatic polyester.

The aromatic polyester is usually crystalline, and can be formed from, for example, an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol.
Examples of the aromatic polyester include polyethylene terephthalate, polybutylene terephthalate, polystyrene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, and polybutylene terephthalate is preferable.

  One of the aromatic polyesters includes terephthalic acid and / or polybutylene terephthalate derived from dimethyl terephthalate and 1,4-butanediol, and further, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid A dicarboxylic acid component such as naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or an ester-forming derivative thereof, and a molecular weight of 300 or less Diol [for example, aliphatic diol such as ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, 1,4-cyclohexanedimethanol, tricyclodecane dimethylol Such as alicyclic diol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4′-dihydroxy-p-terphenyl, 4,4′-dihydroxy-p-quarterphenyl It may be a polyester derived from an aromatic diol, etc.], or a copolyester in which two or more of these dicarboxylic acid components and diol components are used in combination. It is also possible to copolymerize a trifunctional or higher polyfunctional carboxylic acid component, polyfunctional oxyacid component, polyfunctional hydroxy component, and the like in a range of 5 mol% or less.

  As the polyester-based thermoplastic resin that is not an elastomer as described above, a commercially available product may be used. For example, “Duranex” series (for example, 2000, 2002, etc.) manufactured by Polyplastics Co., Ltd., Mitsubishi Engineering Plastics Co., Ltd. ) NOVADURAN series (for example, 5010R5, 5010R3-2, etc.) manufactured by Toray Industries, Inc. and “Trecon” series (for example, 1401X06, 1401X31, etc.) manufactured by Toray Industries, Inc.

  As the aliphatic polyester, both a dicarboxylic acid / diol condensation system and a hydroxycarboxylic acid condensation system are used. Examples thereof include polylactic acid, polyhydroxy-3-butylbutyric acid, polyhydroxy-3-hexylbutyric acid, poly (ε-caprolactone), polyenanthlactone, polycaprylolactone, polybutylene adipate, polyethylene adipate, and the like. Polylactic acid is a typical resin as a biodegradable plastic, and a preferred embodiment of polylactic acid will be described later.

(Dynamic cross-linked thermoplastic elastomer)
Moreover, you may use a dynamic bridge | crosslinking type thermoplastic elastomer as a resin material.
The dynamic crosslinkable thermoplastic elastomer is a thermoplastic elastomer produced by mixing a rubber into a molten thermoplastic resin, adding a crosslinker and kneading the rubber component under kneading conditions.
Hereinafter, the dynamically crosslinked thermoplastic elastomer is sometimes simply referred to as “TPV” (Thermo Plastic Vulcanizate elastomer).

Examples of the thermoplastic resin that can be used for the production of TPV include the thermoplastic resins described above (including thermoplastic elastomers).
Examples of rubber components that can be used in the production of TPV include diene rubbers and hydrogenated products thereof (for example, NR, IR, epoxidized natural rubber, SBR, BR (high cis BR and low cis BR), NBR, hydrogenated NBR, Hydrogenated SBR), olefin rubber (for example, ethylene propylene rubber (EPDM, EPM), maleic acid modified ethylene propylene rubber (M-EPM), IIR, isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber ( ACM), ionomers), halogen-containing rubbers (for example, Br-IIR, Cl-IIR, brominated products of isobutylene paramethylstyrene copolymer (Br-IPMS), chloroprene rubber (CR), hydrin rubber (CHR), chlorosulfonated Polyethylene (CSM), chlorinated polyethylene (CM), maleic acid modified Plain polyethylene (M-CM), silicone rubber (eg, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber), sulfur-containing rubber (eg, polysulfide rubber), fluorine rubber (eg, vinylidene fluoride rubber) Fluorine-containing vinyl ether rubbers, tetrafluoroethylene-propylene rubbers, fluorine-containing silicone rubbers, fluorine-containing phosphazene rubbers), etc., and in particular, isobutylene-isoprene copolymer having a halogen group introduced therein as a modified polyisobutylene rubber. Polymeric rubber and / or halogen-containing copolymer rubber of isomonoolefin and p-alkylstyrene such as isobutylene-paramethylstyrene copolymer rubber having a halogen group introduced therein can be used effectively. Exxpro "is preferably used.

  Various additives such as rubber, various fillers (for example, silica, calcium carbonate, clay), anti-aging agents, oils, plasticizers, colorants, weathering agents, and reinforcing materials are added to the resin material as desired. You may make it contain. The content of the additive in the resin material is not particularly limited, and can be appropriately used as long as the effects of the present invention are not impaired. When a component other than a resin such as an additive is added to the resin material, the content of the resin component in the resin material is preferably 50% by mass or more, and more preferably 90% by mass or more based on the total amount of the resin material. The content of the resin component in the resin material is the balance obtained by subtracting the total content of various additives from the total amount of the resin component.

The resin material for the tire frame member and the resin material for the coating layer are not particularly limited as long as they are the resin materials described above, and various materials can be used depending on the purpose.
For example, since the coating layer covers the tire frame member and is formed from the bead portion to the tread portion, that is, the side portion, it is easily bent when receiving a shock when the tire is used. Therefore, it is preferable that the resin material for coating layers is a resin material which is excellent in followability and rich in flexibility. Moreover, since a coating layer is exposed to external air instead of a tire frame member, it is preferable that it is excellent in a weather resistance rather than a tire frame member. Furthermore, in order to prevent air leakage from the tire, the resin material for the coating layer is preferably excellent in sealing properties.
Next, the preferable physical property of the resin material which comprises a tire frame member and a coating layer is demonstrated.

(Physical properties of resin materials)
First, preferable physical properties will be described as a resin material for a tire frame member.
-Tensile modulus-
As a tensile elasticity modulus prescribed | regulated to JISK7113: 1995 of the resin material for tire frame members, 100 MPa-1000 MPa are preferable, 100 MPa-800 MPa are more preferable, 100 MPa-700 MPa are especially preferable. When the elastic modulus of the resin material is 100 MPa to 700 MPa, the rim can be assembled efficiently while maintaining the shape of the tire frame.

  The elastic modulus of the resin material for the coating layer is preferably 0.5 MPa to 100 MPa. When the elastic modulus of the resin material for the coating layer is 0.5 MPa or more, when the coating layer is in close contact with the rim, the compressive creep property of the close contact portion is excellent, and a gap is hardly formed between the coating layer and the rim. When the elastic modulus of the resin material for the coating layer is 100 MPa or less, the contact portion between the coating layer and the rim is easily compressed and deformed, and a gap is hardly formed between the coating layer and the rim.

Further, the tensile elastic modulus defined in JIS K7113: 1995 of the resin material for the coating layer is more preferably 70% or less of the elastic modulus of the tire frame member. Thereby, between the rim | limbs 20 can be sealed appropriately, maintaining the rigidity of the tire frame member 17. FIG.
The elastic modulus of the resin material for the coating layer is more preferably 50% or less of the elastic modulus of the resin material for the tire frame member, and when a resin material having excellent wear resistance is used as the resin material for the coating layer Is more preferably 25% or less.

-Tensile yield strength-
The tensile yield strength specified in JIS K7113: 1995 of the resin material for tire frame members is preferably 5 MPa or more, preferably 5 MPa to 20 MPa, and more preferably 5 MPa to 17 MPa. When the tensile yield strength of the resin material for a tire frame member is 5 MPa or more, the tire frame member can withstand deformation against a load applied to the tire during traveling.

-Tensile yield elongation-
The tensile yield elongation specified in JIS K7113: 1995 of the resin material for tire frame members is preferably 3% or more, preferably 3% to 70%, and more preferably 3% to 60%. When the tensile yield elongation of the resin material is 10% or more, the elastic region is large, and the rim assembly property can be improved.
The tensile yield elongation defined in JIS K7113: 1995 of the resin material for the coating layer is preferably 3% or more.

-Tensile elongation at break-
The tensile elongation at break specified in JIS K7113: 1995 of the resin material for tire frame members is preferably 50% or more, preferably 100% or more, more preferably 150% or more, and particularly preferably 200% or more. When the tensile elongation at break of the resin material is 50% or more, the rim assembly property is good and it is possible to make it difficult to break against a collision.
The tensile elongation at break specified in JIS K7113: 1995 of the resin material for the coating layer is preferably 50% or more.

− Deflection temperature under load −
As a deflection temperature under load (0.45 MPa load) specified in ISO75-2 or ASTM D648 of a resin material for a tire frame member, 50 ° C or higher is preferable, 50 ° C to 150 ° C is preferable, and 50 ° C to 130 ° C is preferable. Further preferred. When the deflection temperature under load of the resin material is 50 ° C. or higher, deformation of the tire frame member can be suppressed even when vulcanization is performed in the manufacture of the tire.

  Furthermore, it is preferable that the Vicat softening temperature (A method) prescribed | regulated to JISK7113 of the resin material for coating layers is 130 degreeC or more.

Further, the melting point (or softening point) of the resin material itself is usually 100 ° C. to 350 ° C., preferably about 100 ° C. to 250 ° C., but preferably about 120 ° C. to 250 ° C. from the viewpoint of tire productivity. 120 ° C to 200 ° C is more preferable.
In this way, by using a resin material having a melting point of 120 ° C. to 250 ° C., for example, when a tire skeleton is formed by fusing the divided bodies (frame pieces), the periphery of 120 ° C. to 250 ° C. Even if the frame body is fused in the temperature range, the bonding strength between the tire frame pieces is sufficient. For this reason, the tire of this invention is excellent in durability at the time of driving | running | working, such as puncture resistance and abrasion resistance. The heating temperature is preferably 10 ° C to 150 ° C higher than the melting point (or softening point) of the resin material forming the tire frame piece, and more preferably 10 ° C to 100 ° C higher.

The resin material can be obtained by adding various additives as necessary and mixing them appropriately by a known method (for example, melt mixing).
The resin material obtained by melt mixing can be used in the form of pellets if necessary.

[Protective layer]
It is preferable that a transparent protective layer is further laminated on the decorative portion on the surface of the coating layer.
A structural example of the protective layer will be described with reference to FIG.
As shown in FIG. 6, a protective layer 36 is laminated on the covering layer 24. In FIG. 6, the protective layer 36 covers from the bead portion 12 to the end portion 30 </ b> A in the tire axial direction of the tread portion 30, but only the decorative portion (not shown) on the covering layer 24. The structure which coat | covers may be sufficient.
Since the protective layer 36 covers at least the decorative portion, it is possible to suppress discoloration of the decorative portion or to make it difficult to be lost even when the tire is exposed to wind and rain or receives an impact. The appearance of the part can be maintained for a long time.

  In particular, since the tire is used in an environment where it is exposed to wind and rain and heated by direct sunlight, depending on the type of resin material constituting the coating layer 24, hydrolysis may occur, but the tire is covered with a protective layer 36. Thus, since the deterioration of the covering layer 24 can be suppressed, discoloration and deformation of the decorative portion accompanying the deterioration of the covering layer 24 can also be suppressed.

  Since the protective layer 36 is a member that covers at least the decorative portion, the protective layer 36 needs to be transparent to the extent that the decorative portion can be visually recognized through the protective layer 36 even after the protective layer 36 is laminated on the decorative portion. There is. More specifically, the protective layer 36 has a light (visible light) transmittance of 70% or more. The light transmittance of the protective layer 36 is a value measured using a spectrophotometer.

  In addition, the protective layer 36 is formed on the side portion 14 similarly to the covering layer 24, and is frequently bent during use of the tire and easily receives an impact. Therefore, the protective layer 36 is preferably rich in flexibility to follow the covering layer 24. Examples of such a protective layer material that is transparent and excellent in flexibility include a material containing a thermoplastic resin. Thermoplastic resins include polyolefin-based thermoplastic elastomer (TPO), polystyrene-based thermoplastic elastomer (TPS), polyamide-based thermoplastic elastomer (TPA), polyurethane-based thermoplastic elastomer (TPU), and polyester-based thermoplastic elastomer (TPC). , And dynamically cross-linked thermoplastic elastomers (TPV), non-elastomer polyolefin-based thermoplastic resins, non-elastomer polystyrene-based thermoplastic resins, non-elastomer polyamide-based thermoplastic resins, non-elastomer-based polyester thermoplastic resins, and the like Is mentioned. Specific examples of these thermoplastic resins are the same as the specific examples of the thermoplastic resin described as the resin material constituting the coating layer and the tire frame member.

The protective layer 36 may be formed during the manufacture of the tire, or may be formed after the tire is completed. Although details of the tire manufacturing method will be described later, the tire frame member 17 made of a resin material forms the tire frame half body 17A by, for example, injection molding, and forms the coating layer 24 on the outer surface of the tire frame half body 17A. . Next, the two tire skeleton halves 17A on which the coating layer 24 is formed are abutted against each other at the tire equator plane CL (tire center), and the two tire skeleton halves 17A are joined together, thereby the tire skeleton member. 17 is manufactured. Furthermore, the cord is spirally wound around the outer peripheral surface of the tire frame member 17 to form the reinforcing layer 28, and the tread portion main body 32 is bonded to the tread portion 30 and vulcanized to complete the tire.
At this time, the protective layer 36 may be laminated on the coating layer 24 of the tire frame half body 17A on which the coating layer 24 is formed, or the tire frame member 17 obtained by joining the two tire frame half bodies 17A. It may be laminated on the coating layer 24. Further, the protective layer 36 may be laminated on the coating layer 24 after the vulcanized tread is adhered to the tire frame member 17, that is, after completion.

  The protective layer 36 may be formed on the coating layer 24 by extrusion molding or injection molding of a protective layer material containing the above-described thermoplastic resin. Moreover, a transparent resin film may be bonded on the coating layer 24 using an adhesive, or an adhesive resin film may be laminated on the coating layer 24. Furthermore, a film cured by UV irradiation or heating after laminating an ultraviolet (UV) curable or thermosetting film on the coating layer 24 may be used as the protective layer 36. When a resin film that shrinks by heating is used as the material for the protective layer, the adhesion to the coating layer 24 and the followability are excellent.

In particular, when a film that crosslinks and cures by UV irradiation and adheres to the coating layer 24 is used to form the protective layer 36, a large-scale apparatus or the like is not required, and the process can be easily performed.
When an adhesive film that is crosslinked by UV irradiation is used as the material for the protective layer, examples of components constituting the UV-crosslinkable adhesive film include urethane acrylate, polyester acrylate, acrylic resin, epoxy resin, and oxetane resin. , Silicone resin, imide resin and the like.

  The protective layer material may further contain various additives such as anti-aging agent, oil, plasticizer, weathering agent, reinforcing material, monomer, oligomer, reactive diluent, initiator and the like. The content of the additive in the protective layer material is not particularly limited, and can be appropriately used as long as the transparency and flexibility of the protective layer 36 are not impaired. When a component other than a resin such as an additive is added to the protective layer material, the content of the additive in the protective layer material is preferably 50% by mass or less, and preferably 10% by mass or less based on the total amount of the protective layer material. Is more preferable.

  As described above, the resin material constituting the coating layer 24 may also contain an additive such as an anti-aging agent. However, the anti-aging agent is contained in the coating layer 24 more than in the protective layer 36. Can be reduced. This is because the protective layer 36 contains an anti-aging agent and the deterioration of the coating layer 24 is also suppressed by suppressing the deterioration.

  Further, the protective layer 36 preferably has an elastic modulus of 0.5 MPa or more and 100 MPa or less, a tensile yield elongation similarly defined by JIS K7113 is 3% or more, and a tensile fracture elongation similarly defined by JIS K7113 is 50. % Or more is preferable.

[Tire and tire manufacturing method]
Hereinafter, a tire according to an embodiment and a manufacturing method thereof will be described with reference to the drawings.

The tire 10 of this embodiment will be described. 1A is a cross-sectional view of a pneumatic tire, and FIG. 1B is a partially enlarged perspective cross-sectional view when the pneumatic tire is mounted on a rim.
As shown in FIG. 1A, the tire 10 of the present embodiment is formed on the outer side of the tire frame member 17 from the bead portion 12 to the tread portion 30 and the tire frame member 17 having the tread portion 30 and the bead portion 12. And a coating layer 24 having a decorative portion on the surface.
As shown in FIG. 1B, each of the pair of bead portions 12 is in close contact with the bead seat portion 21 and the rim flange 22 of the rim 20 to maintain the internal pressure of the air filled in the tire. A tread portion 30 that constitutes a tire tread that is a ground contact portion of the tire is disposed on the outer side in the tire radial direction of the crown portion 16.

  The tire frame member 17 is made of a resin material (for example, a polyamide-based thermoplastic elastomer; “UBESTA XPA9048X1” manufactured by Ube Industries, Ltd.). Further, the tire frame member 17 has an annular tire frame half body 17A having the same shape in which one bead portion 12, one side portion 14, and a half-width crown portion 16 are integrally formed so as to face each other. It is formed by joining at the tire equatorial plane CL. For joining at the tire equatorial plane CL, a thermoplastic material 19 for welding is used. The tire frame member 17 is not limited to a member formed by joining two members, but may be formed by joining three or more members, a pair of bead portions 12, a pair of side portions 14, The crown portion 16 may be integrally formed.

As shown in FIG. 2, a tire frame step 18 may be formed on the outer surface of the tire frame member 17. The tire frame step portion 18 can be used as a weir for preventing the outflow of the resin material, because the coating layer 24 is formed by injection molding of the resin material. Thereby, it can suppress that the resin material for coating layers flows out of a predetermined | prescribed metal mold | die position, and flows out in the edge part of the coating layer 24, and formation of the edge part of the coating layer 24 can be performed appropriately. .
The tire skeleton step portion 18 constitutes a wall surface rising from the surface of the tire skeleton member 17, and may be constituted by a step or may be constituted by a convex portion. . Further, the angle between the surface of the tire frame member 17 and the wall surface may be smaller than 90 degrees.

  In the present embodiment, the tire frame step 18 is formed on the tire equatorial plane side with respect to the end 30A of the tread portion 30 in the tire axial direction. The tire frame step portion 18 is a step portion formed on the surface of the tire frame member 17 so that the bead portion 12 side is lowered, and is integrally formed on the outer surface of the tire frame member 17. The tire frame step portion 18 is a portion that defines a boundary with a coating layer 24 described later. The thickness of the tire frame member 17A on the inner side in the tire axial direction W than the tire frame step portion 18 is thicker than the thickness of the tire frame member 17A on the outer side in the tire axial direction W.

  In the present embodiment, the tire frame step portion 18 is configured by a step, but the tire frame step portion 18 may be formed by a ridge extending along the entire circumference in the tire circumferential direction.

  The height H1 of the tire frame step 18 is preferably 0.2 mm or greater and 4.0 mm or less. When the height H1 of the tire frame step portion 18 is less than 0.2 mm, when the coating layer 24 is injection-molded as will be described later, the effect of blocking the coating layer material injected at a high pressure is reduced. This is because if it exceeds 0 mm, the thickness of the coating layer 24 becomes too thick.

  The tire skeleton half body 17A formed using a plastic material can be formed by, for example, vacuum forming, pressure forming, injection forming, melt casting, etc. Compared to the case of forming (vulcanizing) with rubber, The manufacturing process can be greatly simplified and the molding time can be shortened.

  An annular bead core 15 is embedded in the bead portion 12 of the tire frame member 17. The bead core 15 is made of a steel cord similar to a conventional general pneumatic tire. Note that the bead core 15 may be omitted if the rigidity of the bead portion 12 is ensured and there is no problem in fitting with the rim 20. The bead core 15 may be formed of a cord other than steel, such as an organic fiber cord or a cord coated with an organic fiber, and the bead core 15 is not formed of a cord but is formed of a hard resin by injection molding or the like. It may be.

  A reinforcing layer 28 having a steel cord 26 wound in a spiral shape is embedded in the crown portion 16 of the tire frame member 17. The reinforcing layer 28 corresponds to a belt disposed on the outer peripheral surface of the carcass of a conventional rubber pneumatic tire. The end 28A in the tire axial direction of the reinforcing layer 28 is disposed closer to the tire equatorial plane CL than the tire frame step 18 is. Thus, the end surface 24A of the covering layer 24 is disposed outside the reinforcing layer 28 in the tire axial direction W, and the reinforcing layer 28 is prevented from being covered with the covering layer 24, and the reinforcing layer 28 is treaded outward in the tire radial direction. The parts 30 can be appropriately stacked.

A coating layer 24 is formed on the tire frame member 17 from the bead portion 12 to the tread portion 30. The covering layer 24 is made of a resin material (for example, polyurethane-based thermoplastic elastomer; “Elastolan ET680” manufactured by BASF).
As shown in FIG. 2, the end portion of the coating layer 24 on the bead portion 12 side is disposed so as to extend to the tire inner side than the close contact portion of the bead portion 12 with the rim 20. The end of the coating layer 24 on the tread portion 30 side is formed up to the tire frame step 18, and the end surface 24 </ b> A is in close contact with the tire frame step 18. When the tire 10 is assembled to the rim 20, the coating layer 24 is in close contact with the rim 20 and seals the gas-filled space in the tire 10. Moreover, the side part and bead part of a tire frame member can also be formed by separate members depending on the performance required for the tire.

  As shown in FIG. 5, the tread portion 30 is disposed on the outer side in the tire radial direction of the tire frame member 17. The tread portion 30 is disposed along the tire frame member 17 and constitutes a tire tread that is a ground contact portion of the tire 10. The tread portion 30 includes a tread portion main body 32 and an intermediate rubber 34. The tread portion main body 32 is laminated on the tire frame member 17 via an intermediate rubber 34. An end 30A in the tire axial direction of the tread portion 30 is disposed on the outer side in the tire axial direction with respect to the end surface 24A of the coating layer 24. As a result, the end surface 24 </ b> A of the covering layer 24 is covered with the tread portion 30, and the entire outer surface from the bead portion 12 to the tread portion 30 of the tire frame member 17 is covered with the covering layer 24.

On the surface of the covering layer 24, a decoration portion (not shown) is formed by using a known ink and a decoration made up of a mark made up of characters “BRIDGESTONE” and a decoration made up of trees and animals. .
The polyurethane-based thermoplastic elastomer, which is a resin material for the coating layer used in the present embodiment, has flexibility and durability against repeated bending accompanying tire rolling, and the ink is easily adapted and easily decorated. .
Since the coating layer 24 is made of a resin material such as a polyurethane-based thermoplastic elastomer, the polyurethane-based thermoplastic elastomer can be colored even when the resin material contains an anti-aging agent, so that the anti-aging agent is likely to precipitate. Compared with the case where it is comprised with rubber | gum, discoloration of a decoration part is suppressed and the external appearance of a decoration part can be maintained.

  The tread portion 30 is made of rubber that has better wear resistance than the thermoplastic resin forming the side portion 14. As the rubber used for the tread portion 30, the same type of rubber as that used in conventional rubber pneumatic tires can be used. In addition, as the tread part 30, you may use what is comprised with the other kind of thermoplastic resin which is more excellent in abrasion resistance than the thermoplastic resin which forms the side part 14. FIG.

Moreover, it is preferable that a transparent protective layer is provided on the decorative portion on the surface of the coating layer 24.
The tire 90 of the present embodiment shown in FIG. 6 is the same as the embodiment of the tire 10 except that a transparent protective layer is laminated on the covering layer. In the present embodiment, the same parts as those of the embodiment of the tire 10 are denoted by the same reference numerals, and detailed description thereof is omitted.

As shown in FIG. 6, the tire 90 of the present embodiment is formed on the surface of a tire frame member 17 having a tread portion 30 and a bead portion 12 and on the outer surface of the tire frame member 17 from the bead portion 12 to the tread portion 30. And a coating layer 24 having a decorative portion. A protective layer 36 is laminated on the covering layer 24 to cover the bead portion 12 and the end portion 30A of the tread portion 30 in the tire axial direction.
Since the protective layer 36 covers the decorative portion, the external damage resistance of the covering layer 24 is improved and the discoloration of the decorative portion is suppressed, so that the appearance of the decorative portion can be maintained for a long time.
The protective layer 36 can be easily formed after completion of the tire by using, for example, a UV crosslinkable adhesive coating agent (urethane acrylate coating agent), and is made of a polyurethane-based thermoplastic elastomer. It is easy to adhere to the covering layer 24.

  Next, a method for manufacturing the tire 10 according to the present embodiment will be described.

In the present embodiment, first, the tire frame half body 17A is formed by injection molding. The bead core 15 is disposed in a mold for forming a tire frame half body during the injection molding, and is embedded in each of the pair of bead portions 12.
The tire frame half body 17A is made of a resin material, and for example, a polyamide-based thermoplastic elastomer (“UBESTA XPA9048X1” manufactured by Ube Industries) is used.

  Next, the coating layer 24 is formed on the outer surface of the tire frame half body 17A. For manufacturing the coating layer 24, a coating layer forming mold 70 as shown in FIG. 3 is used. The covering layer 24 is made of a resin material, and for example, a polyurethane-based thermoplastic elastomer (“Elastolan ET680” manufactured by BASF) is used.

  The coating layer forming mold 70 includes an outer mold 72 and an inner mold 74, and a gate 78 for injecting a coating layer material is formed in the outer mold 72. The gate 78 is configured to inject the thermoplastic material for the coating layer from the radially inner side of the bead portion 12 of the tire frame half body 17A. As the gate 78, multiple pin gates may be provided in the circumferential direction of the tire frame half body 17A, or a disk gate opened in a ring shape may be used.

  When the tire skeleton half body 17A is accommodated in the coating layer forming mold 70 and completely closed, as shown in FIG. 4, a set shape that communicates with the gate 78 between the outer mold 72 and the tire skeleton half body 17A. The space Z1 for forming the coating layer 24 is formed.

  On the outer mold 72 and the inner mold 74, a convex portion 72A and a concave portion 74A are formed on the respective split surfaces on the side where the bead portion 12 is disposed. Moreover, the recessed part 72B and the convex part 74B are comprised in the division surface by the side of the centerline CL. The convex part 72A of the outer mold 72 is fitted into the concave part 74A of the inner mold 74, the convex part 74B of the inner mold 74 is fitted into the concave part 72B of the outer mold 72, and the parting surfaces contact each other. Then, the coating layer forming mold 70 is closed.

  The coating layer forming mold 70 has a vent hole (not shown) for expelling air in the cavity when the coating layer material is injected into the cavity.

  In order to form the coating layer 24, as shown in FIG. 4, the tire frame half body 17A is set in the inner mold 74, and the projection 72A of the outer mold 72 is fitted into the recess 74A of the inner mold 74. The convex portion 74B of the inner mold 74 is fitted into the concave portion 72B of the outer mold 72, and the dividing surface is closed.

  In this state, the coating layer material is injected from the gate 78 into the cavity. At this time, the material for the coating layer injected from the gate 78 is blocked by the tire frame step portion 18, and the outflow from the space Z1 is suppressed. Therefore, the coating layer 24 can be accurately formed at a predetermined position. Moreover, the internal pressure of the space Z1 at the time of injection molding is maintained, and the coating layer 24 can be appropriately bonded to the tire frame member 17.

  Thereafter, the tire frame half body 17A is taken out from the coating layer forming mold 70. Thereby, the tire frame half body 17 </ b> A having the coating layer 24 is formed.

  In addition, in order to increase the bonding strength between the surface of the bead portion 12 of the tire frame half body 17A and the coating layer 24, the surface of the bead portion 12 is formed into an uneven shape so that the anchor effect (anchor is lowered as the anchor is lowered) is engaged. Effect) may be obtained. The depth of the unevenness for obtaining such an anchor effect is preferably 2 mm or less, and more preferably 1 mm or less. If it is deeper than 2 mm, the strength of the molded product may be reduced. Further, if the depth of the unevenness is shallower than 0.05 mm, it is difficult to obtain a sufficient anchor effect. In order to form such an uneven shape, an uneven shape corresponding to the molding surface of the mold 40 may be formed in advance. The irregularities may be formed by roughening the surface by buffing.

  Further, in order to increase the bonding strength between the surface of the tire frame half body 17A and the coating layer 24, an adhesive may be applied to the surface of the portion of the tire frame half body 17A where the coating layer 24 is formed. In this case, if the surface of the part to which the adhesive is applied is buffed with sandpaper or the like, the adhesive force is improved. Moreover, in order to improve adhesive force, it is preferable to dry to some extent after apply | coating an adhesive agent. For this reason, when apply | coating an adhesive agent, it is preferable to carry out in the atmosphere of 70% or less of humidity. The adhesive is, for example, a triazine thiol adhesive, but is not particularly limited, such as a chlorinated rubber adhesive, a phenol resin adhesive, an isocyanate adhesive, and a halogenated rubber adhesive.

  Next, the two tire skeleton halves 17A on which the coating layer 24 is formed are abutted against each other at the tire equatorial plane CL (tire center), and the welding thermoplastic material 19 (see FIG. 1) is joined to each other. The two tire skeleton halves 17A are joined. Thereby, the tire frame member 17 in which the coating layer 24 is formed from the bead portion 12 to the tread portion 30 is manufactured.

  In this embodiment, the two tire skeleton halves 17A are joined after the formation of the coating layer 24. However, the two tire skeleton halves 17A are joined first, and then the coating layer 24 is formed. Also good.

  Thereafter, while rotating the tire frame member 17 with a rotating device, a heated cord 26 discharged from a cord supply device (not shown) is spirally wound around the outer peripheral surface of the tire frame member 17 to form a reinforcing layer 28. To do.

  Thereafter, a tread portion main body 32 that is a precure tread (PCT) is bonded to the outside of the reinforcing layer 28. The tread portion main body 32 can be bonded by vulcanization bonding via the intermediate rubber 34.

At the time of vulcanization adhesion, as shown in FIG. 5, an unvulcanized intermediate rubber 34 is laminated on the reinforcing layer 28 of the tire frame member 17, and the tread portion main body 32 is wound around the outer side by one turn. At this time, the end portions in the tire axial direction of the tread portion main body 32 and the unvulcanized intermediate rubber 34 are arranged so as to overlap the end portions of the coating layer 24 and cover the end surface 24A.
Next, the bead part 12 is assembled | attached to a pair of cyclic | annular support member which has a structure close | similar to a rim | limb, and it puts in a vulcanizer and vulcanizes.
As described above, the tread portion 30 is formed.

Next, a decorative portion on which a mark and a decoration are drawn is formed on the surface of the coating layer 24. For example, the characters “BRIDGESTONE”, trees, and animals can be drawn on the surface of the coating layer 24 using an inkjet recording apparatus.
Further, for example, a transparent protective layer 36 is formed by laminating a UV-crosslinkable adhesive film (urethane acrylate film) on the coating layer 24 so that at least the decorative portion is covered and irradiating with UV. And the decorative part can be easily protected.

  As described above, the decoration on the surface of the coating layer 24 may be performed at any time after the coating layer 24 is formed on the tire frame member 17 and is performed after the tire is completed as in this embodiment. Alternatively, it may be performed before joining the tire frame member half body 17A. The protective layer 36 may be formed at any time after the surface of the covering layer 24 is decorated, may be performed after the tire is completed as in the present embodiment, or the tire frame member half body 17A may be formed. You may carry out before joining.

  The tire 10 or the tire 90 is manufactured through the above steps. The tread portion main body 32 before vulcanization adhesion may be completely vulcanized or semi-vulcanized.

  As described above, in the present embodiment, since the coating layer 24 is formed from the bead portion 12 of the tire frame member 17 to the end portion 30A of the tread portion 30, exposure of the tire frame member 17 is avoided. Therefore, the tire frame member 17 can be protected while maintaining physical properties such as rigidity required for the tire frame member 17 itself, and the weather resistance of the tire 10 can be improved. Furthermore, since the coating layer 24 is made of a resin material and does not need to use a member that suppresses precipitation of the anti-aging agent, the weight of the tire can be suppressed, and the discoloration of the decorative portion by the anti-aging agent can be suppressed. Is suppressed, and the appearance of the decorative portion can be obtained.

  The embodiments of the present invention have been described above with reference to the embodiments. However, these embodiments are merely examples, and various modifications can be made without departing from the scope of the invention, and the order of the manufacturing steps can be changed as appropriate. Is possible. It goes without saying that the scope of rights of the present invention is not limited to these embodiments.

DESCRIPTION OF SYMBOLS 10 Tire 12 Bead part 17 Tire frame member 24 Coating layer 30 Tread part 36 Protective layer 90 Tire

Claims (2)

A tire frame member made of a resin material and having at least a tread portion and a bead portion;
A coating layer made of a resin material, formed on the outside of the tire frame member from the bead portion to the tread portion, and having a decoration portion on the surface;
With tires. The tire according to claim 1, further comprising a transparent protective layer laminated on at least the decorative portion.