WO2008069183A1 - オキシメチレン系重合体を含む樹脂材料の接着方法および構造体 - Google Patents

オキシメチレン系重合体を含む樹脂材料の接着方法および構造体 Download PDF

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Publication number
WO2008069183A1
WO2008069183A1 PCT/JP2007/073344 JP2007073344W WO2008069183A1 WO 2008069183 A1 WO2008069183 A1 WO 2008069183A1 JP 2007073344 W JP2007073344 W JP 2007073344W WO 2008069183 A1 WO2008069183 A1 WO 2008069183A1
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WO
WIPO (PCT)
Prior art keywords
resin material
oxymethylene polymer
oxymethylene
polymer composition
peak
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/073344
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English (en)
French (fr)
Inventor
Akira Okamura
Satoshi Nagai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to KR1020097010870A priority Critical patent/KR101359283B1/ko
Priority to JP2008548281A priority patent/JPWO2008069183A1/ja
Priority to EP07832964A priority patent/EP2098577B1/en
Priority to CN2007800441411A priority patent/CN101611111B/zh
Priority to US12/517,472 priority patent/US8377250B2/en
Publication of WO2008069183A1 publication Critical patent/WO2008069183A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09J159/00—Adhesives based on polyacetals; Adhesives based on derivatives of polyacetals
    • C09J159/02—Polyacetals containing polyoxymethylene sequences only
    • 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
    • C09J159/00—Adhesives based on polyacetals; Adhesives based on derivatives of polyacetals
    • C09J159/04—Copolyoxymethylenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/40—Applying molten plastics, e.g. hot melt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7311—Thermal properties
    • B29C66/73115—Melting point
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7311—Thermal properties
    • B29C66/73115—Melting point
    • B29C66/73116—Melting point of different melting point, i.e. the melting point of one of the parts to be joined being different from the melting point of the other part
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9141—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B29C66/91411—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature of the parts to be joined, e.g. the joining process taking the temperature of the parts to be joined into account
    • 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
    • C09J159/00—Adhesives based on polyacetals; Adhesives based on derivatives of polyacetals
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/721—Fibre-reinforced materials
    • B29C66/7212—Fibre-reinforced materials characterised by the composition of the fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B29C66/91931—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/91—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B29C66/91931—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined
    • B29C66/91935—Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined lower than said fusion temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2059/00—Use of polyacetals, e.g. POM, i.e. polyoxymethylene or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0008—Anti-static agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0026—Flame proofing or flame retarding agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0044—Stabilisers, e.g. against oxydation, light or heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
    • B29K2105/126—Whiskers, i.e. reinforcement in the form of monocrystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2309/00—Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2309/00—Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
    • B29K2309/10—Mica

Definitions

  • the present invention is obtained by a method for bonding a resin material using an oxymethylene polymer having a specific melting point and a melting peak pattern in order to bond resin materials containing the oxymethylene polymer, and the bonding method. Concerning the structure.
  • An oxymethylene polymer is an aliphatic ether type or a polymer mainly composed of an aliphatic ether, and is considered to be a material having a low environmental impact, which is derived from methanol power, which is a raw material independent of petroleum. . It is an excellent material that is currently widely used as engineering plastics with high mechanical properties such as rigidity.
  • an oxymethylene polymer is a resin having high crystallinity, and when bonding between an injection molded product, an extrusion molded product, and a stretched material containing the polymer, a heat history at a high temperature or a long time is required for bonding. After that, the heat shrinkage is larger than expected, and further, the melting on the material side cannot be ignored, and there is a problem that it is impossible to manufacture a structure that maintains the shape accurately.
  • Patent Document 1 Japanese Patent Laid-Open No. 1132638
  • Patent Document 2 JP-A-8-60125
  • Patent Document 3 International Publication 2002-077049
  • the present invention improves the adhesion between resin materials containing an oxymethylene-based polymer and can suppress the thermal shrinkage and thermal deformation of the structure, and the adhesion method. It aims at providing the structure obtained.
  • the inventors of the present invention have compared the melting point of the oxymethylene polymer contained in one resin material when the resin materials containing the oxymethylene polymer are bonded to each other.
  • Heat treatment is performed using a resin material containing an oxymethylene polymer having a specific melting point difference and a melting peak by DSC measurement satisfying a predetermined relationship as (1) the other material or (2) an adhesive layer
  • the present invention has been conceived. As a result, it has been found that the adhesion between materials can be improved without problems such as thermal shrinkage and thermal deformation.
  • the present invention is a resin material bonding method for bonding a resin material (X) containing an oxymethylene polymer (A) and a resin material (Y),
  • Resin material (Y) is an oxymethylene polymer composition that satisfies the following conditions (1) and (2): (B) or
  • the resin material (Y) is a resin material (X) or another type of resin material, and an oxymethylene polymer composition ( ⁇ ) is interposed between the resin material ( ⁇ ) and the resin material (X). This is a method of adhering resin materials to which heat treatment is applied.
  • the oxymethylene polymer composition ( ⁇ ) has a lower melting point than the oxymethylene polymer ( ⁇ ), and the difference in melting point is less than 5 ° C.
  • the peak force indicating the melt state of the oxymethylene polymer composition (B) measured by DSC is also more than 50% of the required peak area.
  • the peak temperature of the oxymethylene polymer (A) is 5 ° C or more lower than the peak temperature. Exists in the temperature range.
  • this invention is a structure obtained by the said adhesion
  • a resin material adhesion method capable of improving the adhesion between resin materials containing an oxymethylene polymer and suppressing the thermal shrinkage and thermal deformation of the structure, and A structure obtained by the bonding method can be provided.
  • the resin material bonding method of the present invention is a method in which the resin material (X) containing the oxymethylene polymer (A) and the resin material (Y) are bonded by heat treatment.
  • the various materials and heat treatment conditions are described below.
  • Examples of the oxymethylene polymer (A) include commercially available les, oxymethylene homopolymers and oxymethylene block copolymers. Among these, a copolymer of trioxane and 0.5 to 30.0 parts by mass of at least one comonomer containing a repeating unit represented by the following general formula (1) is preferable with respect to 100 parts by mass of the trioxane. .
  • the comonomer with respect to 100 parts by mass of trioxane is more preferably from 0.5 to 10.0 parts by mass.
  • R and R each independently represent a hydrogen atom, an alkyl group, an organic group having an alkyl group, a phenyl group, or an organic group having a phenyl group.
  • m represents an integer of;! ⁇ 6.
  • Examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms.
  • Examples of the comonomer include cyclic formal and cyclic ether. Specifically, 1,3-dioxolan and derivatives thereof; 1,3-dioxepane and derivatives thereof; 1,3,5-trioxepane and derivatives thereof; 1,3,6-trioxocane and derivatives thereof; and monofunctional Glycidyl ether is preferred!
  • the oxymethylene polymer (A) in the resin material (X) is preferably 50 vol% or more, and the resin material (X) preferably has an oxymethylene polymer (A) force. ,.
  • the oxymethylene polymer composition (B) contained in the resin material (Y) satisfies the following conditions (1) and (2).
  • the melting point of the oxymethylene polymer composition (B) is lower than that of the oxymethylene polymer (A), and the difference in melting point is less than 5 ° C. When the melting point difference is 5 ° C or more, the component (B) is significantly deformed by melting during bonding.
  • the temperature for bonding becomes very close to the melting point of the oxymethylene polymer (A), and thus the heat shrinkage of the resin material (X). If the thickness is large, there is a risk of damaging the shape due to the force, thermal deformation with the glue, or even melting. It is preferable that 50% or more of the peak area of the oxymethylene polymer composition (B) exists in a temperature range that is 10 ° C or more lower than the peak temperature of the oxymethylene polymer (A). Yes.
  • the oxymethylene-based polymer composition (B) is also represented by the above-mentioned general formula (1), but it is 5.0-50. 0 parts by mass with respect to trioxane and 100 parts by mass of the trioxane. A copolymer with at least one comonomer is preferred. The above comonomer with respect to 100 parts by mass of trioxane is more preferably 10.0 to 5.0 parts by mass.
  • a method may be used in which the comonomer component in the component (B) is distributed.
  • the comonomer component in the component (B) is distributed.
  • two or more oxymethylene polymers having different comonomer contents may be mixed.
  • the polymer composition (B) is preferably 50 vol% or more of the polymer composition (B ) Only.
  • the resin material (Y) does not contain the oxymethylene polymer composition (B), that is, the oxymethylene polymer composition (B) contains the resin material (X) and the resin material (Y).
  • the oxymethylene polymer composition (B) contains the resin material (X) and the resin material (Y).
  • other materials may be used in combination as long as the polymer composition (B) is a main component.
  • the resin material (Y) may be the same material as the resin material (X) or another kind of material.
  • examples of other types of materials include materials having different contents of the oxymethylene-based polymer (A), and materials having components other than the oxymethylene-based polymer (A).
  • the heat treatment conditions are preferably less than the melting point of the oxymethylene polymer (A) and not less than the melting start temperature of the oxymethylene polymer composition (B).
  • the melting point By making the melting point lower than the above melting point, the thermal shrinkage of the material containing the oxymethylene polymer (A) can be suppressed. It is possible to prevent the shape from being damaged due to thermal deformation or even melting. Moreover, sufficient adhesive strength can be provided by setting it as the melting start temperature or more.
  • the temperature be 5 ° C or more lower than the melting point of the oxymethylene polymer (A) and the melting start temperature of the oxymethylene polymer composition (B).
  • the material containing the oxymethylene polymer of the present invention mainly contains the above oxymethylene polymer, but any known additive or the like may be used as long as the original purpose of the present invention is not impaired. It is possible to add a filler.
  • additives include crystal nucleating agents, antioxidants, plasticizers, matting agents, foaming agents, lubricants, mold release agents, antistatic agents, ultraviolet absorbers, light stabilizers, heat stabilizers, Examples include deodorants, flame retardants, sliding agents, fragrances, and antibacterial agents.
  • the filler include glass fiber, talc, my strength, calcium carbonate, and potassium titanate whisker. It is also possible to add pigments and dyes to achieve the desired color. It is also possible to modify by adding various monomers, cutting agents, end treatment agents, other resins, wood flour, starch and the like.
  • the form of the resin material (X) and the resin material (Y) according to the present invention is not limited. I like it.
  • Other examples include, but are not limited to, blow molded products, films, sheets, fibers, multifilaments, monofilaments, ropes, nets, woven fabrics, knitted fabrics, nonwoven fabrics, filters, and materials obtained by secondary processing thereof. It is not something.
  • the oxymethylene polymer (B) is interposed between these materials and thermally bonded, the intervening form is, for example, that the oxymethylene polymer composition (B) is previously applied to the surface of the resin material (A). The ability to exist as a layer or as a domain.
  • the surface containing the oximethylene-based polymer (A) is simultaneously or sequentially applied to the surface in advance. It may be interposed, or may be interposed in the process from the primary processing of the material containing the oxymethylene polymer (A) to the formation of the structure.
  • the structure of the present invention can be obtained by the above-described method for bonding a resin material of the present invention.
  • This structure has good adhesion between resin materials containing an oxymethylene polymer, and heat shrinkage and thermal deformation are suppressed.
  • Such a structure may be used as it is, or may be further processed.
  • the structure once bonded can be bonded to a resin material containing another oxymethylene polymer (A) having a different shape to form a more advanced structure.
  • the layer structure in the case where the structure is a multilayer fiber has two or more layers exposed on the fiber surface in the cross section of the same fiber, and the components constituting the layer are It consists of at least two components of the above resin materials (X) and (Y).
  • the exposure ratio on the surface is not particularly limited, but the exposure ratio of the resin material (Y) (particularly the oxymethylene polymer (B) component) that functions as an adhesive layer during secondary processing is low! Thus, the adhesive strength becomes better. Therefore, the resin material (Y) may be formed as a plurality of separate layers.
  • melter-spun Upital A40 (hereinafter referred to as oxymethylene polymer (a) and! /, U) made by Mitsubishi Engineering Plastics Co., Ltd., which has a melting point of 172 ° C, a draw ratio of 4, a single fineness
  • oxymethylene polymer (a) and! /, U) made by Mitsubishi Engineering Plastics Co., Ltd., which has a melting point of 172 ° C, a draw ratio of 4, a single fineness
  • the molded product processed into 5dtex multifilament was used.
  • resin material (Y) an oxymethylene-based polymer (a) and Upital V40 (hereinafter referred to as resin (b)! ) And are melt blended at a mass ratio of 1: 1, 1: 2, and 3: 1 (referred to as (b-1), (b-2), and (b-3), respectively). Then, a molded product processed into a multifilament with a draw ratio of 1 and a single fineness of 5 dtex was used. [0038] (Measuring method of melting point)
  • the temperature was raised from 30 ° C. to 210 ° C. at a rate of 10 ° C./min, and the melting peak temperature was measured using a differential scanning calorimeter (DSC6200 manufactured by Seiko Instruments Inc.) to obtain the melting point.
  • the ratio of the peak area of the resin material Y in the temperature range 5 ° C and 10 ° C or more lower than the melting peak temperature of the oxymethylene polymer (a) is determined by using the manual split integral analysis mode.
  • the heat absorption (mj / mg) was calculated as the ratio of the endothermic amount in the corresponding region.
  • Resin material (X) multifilament cut to 10 cm length is placed on an iron plate in a straight line, then resin material (Y) multifilament cut to 3 cm length is resin material (X) It was placed at the top so that it intersects with another iron plate. This was subjected to heat bonding treatment (heating treatment) under a heating and pressurizing condition for a predetermined time by a hydraulic hot press apparatus preheated to the temperature shown in Table 1 below.
  • the adhesive state between the resin material (X) and the resin material (Y) was visually confirmed, and each melted and unmelted were confirmed. Further, the length of the resin material (X) after the treatment was measured, and the heat shrinkage ratio before and after the treatment was measured.
  • Resin material (X) (A) and (B). 7k, '1 * «Bg * i * a
  • Example 1 (a) (b-1) 1 56 51 155 90 contact >> Not sensitive 4.9
  • Example 2 (a) (b-1) 1 56 51 160 30 Contact not a 8.7
  • Example 3 (a ) (b-2) 2 64 56 55 90 Adhesive undissolved 4.9
  • Example 4 (a) (b-2) 2 64 56 160 30 Adhesive dissolvable 8.7 Comparative example 1 (a) (b-3) 0 35 25 165 90 No contact * No melt ft-Comparative example 2 (a). (B— 3) 0 35 25 170 30 Adhesion slightly soluble 122 Comparative example 3 (a) (b-3) 0 35 25 175 30 7.1
  • (b-1) a multifilament containing (a) and Upital V40 (resin (b)) having a 155 point of 155 ° C in a 1: 1 (mass ratio) and showing a 171 point of 171 ° C

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Abstract

　オキシメチレン系重合体（Ａ）を含む樹脂材料（Ｘ）と、樹脂材料（Ｙ）とを接着する樹脂材料の接着方法であって、前記樹脂材料（Ｙ）を、下記条件（１）および（２）を満たすオキシメチレン系重合体組成物（Ｂ）とし、あるいは、前記樹脂材料（Ｙ）を、樹脂材料（Ｘ）もしくは他種の樹脂材料とし、当該樹脂材料（Ｙ）と樹脂材料（Ｘ）との間に前記オキシメチレン系重合体組成物（Ｂ）を介在させて、加熱処理を施す樹脂材料の接着方法および当該接着方法により得られる構造体である。 （１）オキシメチレン系重合体組成物（Ｂ）がオキシメチレン系重合体（Ａ）より融点が低く、その融点差が５°C未満である。 （２）ＤＳＣで測定されるオキシメチレン系重合体組成物（Ｂ）の溶融状態を示すピークから求められるピーク面積の５０％以上が、オキシメチレン系重合体（Ａ）のピーク温度より５°C以上低い温度領域に存在する。

Description

明 細 書
ォキシメチレン系重合体を含む樹脂材料の接着方法および構造体 技術分野
[0001] 本発明は、ォキシメチレン系重合体を含む樹脂材料間を接着させるために、特定 の融点および溶融ピークパターンを有するォキシメチレン系重合体を用いる樹脂材 料の接着方法および該接着方法によって得られる構造体に関する。
背景技術
[0002] 近年、地球規模での環境問題に対して、産業廃棄物が環境を汚染することを防止 するために、焼却処理の際に必要な熱量や CO発生量の削減が注目されている。そ の結果、材料の回収、リサイクルについての関心が益々高まっている。
[0003] ォキシメチレン系重合体は、脂肪族エーテル型、もしくは脂肪族エーテルを主成分 としたポリマーであり、主として石油に依存しない原料であるメタノール力 誘導され、 環境負荷の低い材料と考えられている。剛性などの機械的特性も高ぐエンジニアリ ングプラスチックスとして現在、広く使用される優れた材料である。
[0004] ォキシメチレン系重合体を含む樹脂材料同士を接着させる方法としては、その表面 が化学的に不活性なため、超音波融着を行う方法や、ォキシメチレン重合体表面を 予め粗化したり、電子線やプラズマ処理で改質したりした上で、シァノアクリレート系 接着剤、エポキシ系接着剤を用いる方法が知られている。前者はその工程や設備が 複雑であるうえ、適用できる対象も一部の射出成形体に限られている。また、後者は 十分な接着効果が得られないだけでなぐリサイクル性の点で、ォキシメチレン系重 合体とは別の成分を使用することになるために好ましくないといった問題があった。そ のため、ォキシメチレン系重合体を含む樹脂材料同士を同種のォキシメチレン系重 合体の材料で接着する技術が望まれてレ、た。
[0005] ォキシメチレン系重合体同士の接着においては、同系の非晶性共重合体 (特許文 献 1参照）、低融点の共重合体 (特許文献 2参照）の適用が提案されている。前者に ついてはその接着強度が十分でない上に、非晶性共重合体の融点が低ぐ接着後 の耐熱性が劣り、実用性は不十分なものであった。一方、後者は、前者よりも接着強 度が大幅に改良され、接着成分の耐熱性が上がっているものの、接着後に従来のォ キシメチレン系重合体と同じ環境で使用するには未だ耐熱性に劣っている。
[0006] また、ォキシメチレン系重合体は、結晶性の高い樹脂であり、これを含む射出成形 品や押出成形品、延伸材料間の接着に際して、接着のために高温または長時間で の熱履歴を経ると熱収縮が予想以上に大きぐ更には材料側の溶融が無視できなく なり、形状を正確に維持した構造体が製造できないという問題がある。
[0007] 本発明者らは、既にコモノマー含有量の大きいォキシメチレン共重合体を開発して いる。これは、融点が従来のォキシメチレン重合体と比べて適度に低いが、接着剤と して有効性につ!/、てはなんら言及されてレ、な!/、（特許文献 3参照）。
[0008] 特許文献 1：特開平 1 132638号公報
特許文献 2：特開平 8— 60125号公報
特許文献 3 :国際公開 2002— 077049号公報
発明の開示
発明が解決しょうとする課題
[0009] 本発明は、ォキシメチレン系重合体を含む樹脂材料同士の接着性を向上させ、構 造体の熱収縮や熱変形を抑制することが可能な樹脂材料の接着方法、および当該 接着方法により得られる構造体を提供することを目的とする。
課題を解決するための手段
[0010] 本発明者らは、前記課題を解決すべく鋭意検討した結果、ォキシメチレン系重合 体を含む樹脂材料同士を接着させるに際し、一方の樹脂材料に含まれるォキシメチ レン系重合体の融点に対し特定の融点差をもち、 DSC測定による溶融ピークが所定 の関係を満たすォキシメチレン系重合体を含む樹脂材料を、（1)他方の材料として、 または（2)接着層として用いて、加熱処理を行なう本発明に想到した。そして、これに より、熱収縮や熱変形といった問題もなく材料間の接着性を向上させることができるこ とを見出した。
[0011] すなわち、本発明は、ォキシメチレン系重合体 (A)を含む樹脂材料 (X)と、樹脂材 料 (Y)とを接着する樹脂材料の接着方法であって、
樹脂材料 (Y)を、下記条件（1)および (2)を満たすォキシメチレン系重合体組成物 (B)とし、あるいは、
樹脂材料 (Y)を、樹脂材料 (X)もしくは他種の樹脂材料とし、当該樹脂材料 (Υ)と 樹脂材料 (X)との間にォキシメチレン系重合体組成物（Β)を介在させて、加熱処理 を施す樹脂材料の接着方法である。
[0012] (1)ォキシメチレン系重合体組成物（Β)がォキシメチレン系重合体 (Α)より融点が低 ぐその融点差が 5°C未満である。
(2) DSCで測定されるォキシメチレン系重合体組成物（B)の溶融状態を示すピーク 力も求められるピーク面積の 50%以上力 ォキシメチレン系重合体 (A)のピーク温 度より 5°C以上低い温度領域に存在する。
また、本発明は、上記接着方法で得られる構造体である。
発明の効果
[0013] 本発明によれば、ォキシメチレン系重合体を含む樹脂材料同士の接着性を向上さ せ、構造体の熱収縮や熱変形を抑制することが可能な樹脂材料の接着方法、およ び当該接着方法により得られる構造体を提供することができる。
発明を実施するための最良の形態
[0014] [樹脂材料の接着方法]
本発明の樹脂材料の接着方法は、ォキシメチレン系重合体 (A)を含む樹脂材料（ X)と、樹脂材料 (Y)とを加熱処理にて接着する方法である。以下、各種材料および 加熱処理の条件につ!/、て説明する。
[0015] (ォキシメチレン系重合体 (A)を含む樹脂材料 (X) )
ォキシメチレン系重合体 (A)としては、一般に市販されてレ、るォキシメチレンホモポ リマーゃォキシメチレンブロック共重合体などが挙げられる。なかでも、下記一般式（ 1)で示される繰り返し単位を含み、かつ、トリオキサンと該トリオキサン 100質量部に 対し 0. 5-30. 0質量部の 1種以上のコモノマーとの共重合物が好ましい。トリオキサ ン 100質量部に対するコモノマーは、 0. 5—10. 0質量部であることがより好ましい。
[0016] [化 1]
Figure imgf000005_0001
[0017] 上記式（1)中、 R、 Rはそれぞれ独立に、水素原子、アルキル基、アルキル基を有 する有機基、フエ二ル基、フエ二ル基を有する有機基を表す。 mは;!〜 6の整数を表 す。アルキル基としては、炭素数 1〜8のアルキル基が挙げられる。
[0018] 上記コモノマーとしては、環状ホルマールや環状エーテルなどが挙げられる。具体 的には、 1 , 3—ジォキソランおよびその誘導体； 1 , 3—ジォキセパンおよびその誘導 体； 1 , 3, 5—トリオキセパン及びその誘導体； 1 , 3, 6—トリオキソカンおよびその誘 導体；および単官能グリシジルエーテル；が好まし!/、。
[0019] 樹脂材料 (X)中のォキシメチレン系重合体 (A)は、 50vol%以上であることが好ま しく、樹脂材料 (X)がォキシメチレン系重合体 (A)力もなること力 り好ましレ、。
[0020] (樹脂材料 (Y) )
樹脂材料 (Y)に含まれるォキシメチレン系重合体組成物 (B)は、下記条件（1)およ び（2)を満たす。
[0021] (1)ォキシメチレン系重合体組成物（B)の融点は、ォキシメチレン系重合体 (A)より 低ぐその融点差が 5°C未満である。融点差が 5°C以上であると、接着時に (B)成分が 溶融により著しく変形してしまう。
[0022] (2) DSCで測定されるォキシメチレン系重合体組成物（B)の溶融状態を示すピー クから求められるピーク面積の 50%以上力 ォキシメチレン系重合体 (A)のピーク温 度より 5°C以上低い温度領域に存在する。
[0023] また、この溶融ピーク面積の割合が 50%より小さい場合には、接着させるための温 度がォキシメチレン系重合体 (A)の融点に極めて近くなるため、樹脂材料 (X)の熱 収縮が大きくなるば力、りでなぐ熱変形、さらには溶融して形状を損なうおそれがある 。ォキシメチレン系重合体組成物（B)の当該ピーク面積の 50%以上は、ォキシメチ レン系重合体 (A)のピーク温度より 10°C以上低い温度領域に存在することが好まし い。
[0024] ォキシメチレン系重合体組成物（B)中にはォキシメチレン重合体 (A)に近い耐熱 性を有する成分が多く存在することがあるため、上記（1)および（2)の条件を満たす ことで、接着時に (B)成分の溶融による著しい変形が生じたり、充分な接着強度が得 られな!/、と!/、つた問題を回避できる。
[0025] ォキシメチレン系重合体組成物（B)としては、同じく前述の一般式（1)で示されるも のであるが、トリオキサンと該トリオキサン 100質量部に対し 5. 0-50. 0質量部の 1 種以上のコモノマーとの共重合物であることが好ましい。トリオキサン 100質量部に対 する上記コモノマーは、 10. 0-50. 0質量部であることがより好ましい。
[0026] ォキシメチレン系重合体組成物（B)が既述の（1)および（2)の条件を満たすために は、（B)成分内のコモノマー成分に分布を持たせる方法が挙げられ、具体的にはコモ ノマー含有量の異なるォキシメチレン系重合体を 2つ以上混合するなどをすればよい
[0027] 樹脂材料 (Y)がォキシメチレン系重合体組成物 (B)を含有する場合、当該重合体 組成物（B)は、 50vol%以上であることが好ましぐ当該重合体組成物（B)のみで構 成されていることが好ましい。
また、樹脂材料 (Y)がォキシメチレン系重合体組成物 (B)を含有しない場合、すな わち、ォキシメチレン系重合体組成物 (B)が樹脂材料 (X)と樹脂材料 (Y)とを接着 する接着層となる場合は、当該重合体組成物 (B)を主成分とすれば、他の材料を併 用してもよい。
なお、ォキシメチレン系重合体組成物 (B)を接着層とする場合、樹脂材料 (Y)は、 樹脂材料 (X)と同一の材質としてもよぐ他種の材質としてもよい。他種の材質として は、ォキシメチレン系重合物 (A)の含有量が異なる材質、またはォキシメチレン系重 合物 (A)以外の成分が異なる材質などが挙げられる。
[0028] (加熱処理条件）
加熱処理条件 (接着条件）は、ォキシメチレン系重合体 (A)の融点未満で、かつ、 ォキシメチレン系重合体組成物（B)の溶融開始温度以上とすることが好ましレ、。上記 融点未満とすることで、ォキシメチレン系重合体 (A)を含む材料の熱収縮が抑えられ 、熱変形、さらには溶融して形状が損なわれることを防ぐことができる。また、溶融開 始温度以上とすることで、十分な接着強度を付与することができる。
加熱処理条件としては、ォキシメチレン重合体 (A)の融点よりも 5°C以上低い温度 でかつ、ォキシメチレン系重合体組成物（B)の溶融開始温度以上とすることがより好 ましい。
[0029] なお、本発明のォキシメチレン系重合体を含む材料は、主として上記のォキシメチ レン系重合体を含有するものであるが、本発明の本来の目的を損なわない範囲内で 公知の添加剤や充填剤を添加することが可能である。
[0030] 添加剤としては、例えば結晶核剤、酸化防止剤、可塑剤、艷消し剤、発泡剤、潤滑 剤、離型剤、帯電防止剤、紫外線吸収剤、光安定剤、熱安定剤、消臭剤、難燃剤、 摺動剤、香料、抗菌剤等が挙げられる。また、充填剤としては、ガラス繊維、タルク、 マイ力、炭酸カルシウム、チタン酸カリウムウイスカ一等が挙げられる。さらに、顔料、 染料を加えて所望の色目に仕上げることも可能である。また、各種モノマー、カツプリ ング剤、末端処理剤、その他の樹脂、木粉、でんぷんなどを加えて変性することも可 能である。
[0031] さらに、本発明に係る樹脂材料 (X)および樹脂材料 (Y)の形態には限定はないが 、射出成形品、押出成形品、延伸成形、またはそれらを 2次加工した成形品が好まし い。その他に、ブロー成形品、フィルム、シート、繊維、マルチフィラメント、モノフィラメ ント、ロープ、網、織物、編物、不織布、フィルター、更にはそれらを 2次加工した材料 が例示されるが、それらに限定されるものではない。これらの材料間にォキシメチレン 系重合体 (B)を介在させ熱接着させる場合、介在の形態としては、例えば、樹脂材 料 (A)の表面に、予め前記ォキシメチレン系重合体組成物（B)を層状、又はドメイン として存在させること力 S好ましレヽ。
また、連続 (層状、棒状、波打ち状）、もしくは不連続（ドメイン状、ドット状)を問わず 、ォキシメチレン系重合体 (A)を含む材料の 1次加工時に同時に、または逐次的に 表面へ予め介在させてもよいし、ォキシメチレン系重合体 (A)を含む材料の 1次加工 の以後、構造体を形成させるまでの間の工程で介在させてもよい。
[0032] [構造体] 本発明の構造体は、既述の本発明の樹脂材料の接着方法により得られる。この構 造体は、ォキシメチレン系重合体を含む樹脂材料同士の接着性が良好であり、熱収 縮や熱変形が抑制されてレ、る。
[0033] かかる構造体は、そのまま用いてもよいし、さらに加工を施してもしてもよい。例えば 、同じような接着作業をくり返して、もしくは同時に行なうことで、ォキシメチレン系重 合体 (A)を含む少なくとも 1種以上の樹脂材料が多層で構成される構造体とすること もできる。また、一度接着させた構造体を新たに形状の異なる別のォキシメチレン系 重合体 (A)を含む樹脂材料と接着させて更に高度な構造体を形成して!/、くことがで きる。
[0034] 例えば、構造体が多層繊維である場合の層構造としては、同一繊維中、その断面 に、何れも繊維表面に露出した 2つ以上の層を有し、その層を構成する成分が、少な くとも上記の樹脂材料 (X)および (Y)の 2成分からなる。表面への露出割合は、特に 限定されないが、融点が低ぐ 2次加工時に接着層として機能する樹脂材料 (Y) (特 に、ォキシメチレン系重合体 (B)成分）の露出割合が高!/、ほど接着強度は良好なも のとなる。そのため、樹脂材料 (Y)を各々分かれた複数層として形成させてもよい。
[0035] 以下に、実施例を挙げて本発明をさらに具体的に説明する力 本発明は以下に示 す具体例に制限されるものではない。
なお、実施例で使用した材料、融点の測定方法、および接着方法と判断基準とを 以下に示す。
[0036] (樹脂材料）
樹脂材料 (X)として、 172°Cの融点を有する三菱エンジニアリングプラスチック株式 会社製のュピタール A40 (以下、ォキシメチレン系重合体（a)と!/、う）を溶融紡糸し、 延伸倍率 4、単繊度で 5dtexのマルチフィラメントに加工した成形品を使用した。
[0037] 樹脂材料 (Y)として、ォキシメチレン系重合体 (a)と、 155°Cの融点を有する三菱ェ ンジニアリングプラスチックス株式会社製のュピタール V40 (以下、樹脂 (b)と!/、う）と を質量比で、 1 : 1、 1 : 2、 3 : 1の割合で溶融ブレンドしたもの（それぞれ、（b— 1)、 (b — 2)、（b— 3)という）について溶融紡糸し、延伸倍率 1倍、単繊度で 5dtexのマルチ フィラメントに加工した成形品を使用した。 [0038] (融点の測定方法）
10°C/分の速度で、 30°Cから 210°Cまで昇温し、示差走査熱量計 (セイコーインス ツルメンッ (株)製 DSC6200)を用い、溶融ピーク温度を測定し、融点とした。また、 ォキシメチレン系重合体（a)の溶融ピーク温度より 5°Cおよび 10°C以上低い温度領 域における、樹脂材料 Yのピーク面積の割合は手動分割積分の解析モードを用いて ピーク全体の吸熱量 (mj/mg)に対し、該当する領域の吸熱量の割合として求めた。
[0039] (接着方法及び判定基準）
樹脂材料 (X)のマルチフィラメントを 10cm長に切断したものを鉄板の上に直線状 に配置し、次に樹脂材料 (Y)のマルチフィラメントを 3cm長に切断したものを、樹脂 材料 (X)と交差するように上に配置し、更にもう 1つの鉄板で挟みこんだ。これを下記 表 1に記載の温度に予め加熱した油圧式ホットプレス装置によって、所定時間の加 熱、加圧条件下で熱接着処理 (加熱処理)を施した。
[0040] 処理後、樹脂材料 (X)と樹脂材料 (Y)との接着状態を目視で確認し、各々の溶融 、未溶融の確認を行った。また、樹脂材料 (X)の処理後の長さを測定し、処理前後で の熱収縮率を測定した。
[0041] [実施例;!〜 4]
既述の接着方法、および下記表 1に記載の条件で、樹脂材料 (X)と樹脂材料 (Y) とを接着した。評価結果も表 1に示した。
[0042] [比較例;!〜 3]
既述の接着方法、および下記表 1に記載の条件で、樹脂材料 (X)と樹脂材料 (Y) とを接着した。評価結果も表 1に示した。
[0043] [表 1] 【表 1】
特定領域における (B)の溶 ¾
樹脂材料 (Y) ピーク面積の割合 (％)
樹脂材料 (X) (A)と (B)と. 7k、' づ1 * «Bg*i*a
キシメチレン ホツ卜フレスホツ卜ブレス
[ォキシメチレン の敏点差 )の収 温度 (eC) 時間 (分） 接着状態 の樹脂材料 (X 系重合体 (A)] 系重合体組成物 (A)のピーク温 （A)のピーク温
(。c) 度よ tj5°C以上 度よリ10 以上 (X)の状態 縮率 (％)
(B)]
低い温度領域 低い温度領域
実施例 1 (a) (b— 1 ) 1 56 51 155 90 接》 溶敏せず 4.9 実施例 2 (a) (b-1 ) 1 56 51 160 30 接 溶 aせず 8.7 実施例 3 (a) (b-2) 2 64 56 55 90 接着 溶 せず 4.9 実施例 4 (a) (b-2) 2 64 56 160 30 接着 溶》せず 8.7 比較例 1 (a) (b-3) 0 35 25 165 90 接 *せず 溶 ftせず - 比較例 2 (a) . (b— 3) 0 35 25 170 30 接着 やや溶敏 122 比較例 3 (a) (b-3) 0 35 25 175 30 7.1
(a)： 172°Cの S点を るュピタール A40からなるマルチフィラメント
(b-1) :(a)と 155°Cの ¾点を有するュピタール V40(樹脂 (b))とを 1:1 (質量比)で含み、 171°Cの ¾点を示すマルチフィラメント
(b-2)： (a)と樹脂 (b)とを 1 :2 (質量比)で含み、 170。Cの ft点を示すマルチフィラメント
(b-3)： (a)と榭脂 (b)とを 3:1 (»量比〉で含み、 Π2 の飆点を示すマルチフィラメント

Claims

請求の範囲 [1] ォキシメチレン系重合体 (A)を含む樹脂材料 (X)と、樹脂材料 (Y)とを接着する樹 脂材料の接着方法であって、 前記樹脂材料 (Υ)を、下記条件（1)および (2)を満たすォキシメチレン系重合体組 成物（Β)とし、あるいは、 前記樹脂材料 (Υ)を、樹脂材料 (X)もしくは他種の樹脂材料とし、当該樹脂材料（ Υ)と樹脂材料 (X)との間に前記ォキシメチレン系重合体組成物 (Β)を介在させて、 加熱処理を施す樹脂材料の接着方法。
(1)ォキシメチレン系重合体組成物（Β)がォキシメチレン系重合体 (Α)より融点が低 ぐその融点差が 5°C未満である。
(2) DSCで測定されるォキシメチレン系重合体組成物（B)の溶融状態を示すピーク 力も求められるピーク面積の 50%以上力 ォキシメチレン系重合体 (A)のピーク温 度より 5°C以上低い温度領域に存在する。
[2] 条件（2)にお!/、て、 DSCで測定されるォキシメチレン系重合体組成物（B)の溶融 状態を示すピークから求められるピーク面積の 50%以上力 ォキシメチレン系重合 体 (A)のピーク温度より 10°C以上低!/、温度領域に存在する請求項 1に記載の樹脂 材料の接着方法。
[3] 加熱処理の温度を、ォキシメチレン系重合体 (A)の融点未満で、かつ、ォキシメチ レン系重合体組成物（B)の溶融開始温度以上とする請求項 1に記載の樹脂材料の 接着方法。
[4] ォキシメチレン系重合体 (A)が、下記一般式（1)で表される繰り返し単位を含み、 かつ、
トリオキサンと、該トリオキサン 100質量部に対し 0. 5-30. 0質量部の 1種以上の コモノマーとの共重合物である請求項 1に記載の樹脂材料の接着方法。
[化 1]
Figure imgf000012_0001
(式中、
Figure imgf000012_0002
R2はそれぞれ独立に、水素原子、アルキル基、アルキル基を有する有機 基、フエ二ル基、フエ二ル基を有する有機基を表す。 mは 1〜6の整数を表す。 )
[5] ォキシメチレン系重合体組成物（B)が、下記一般式（1 )で表される繰り返し単位を 含み、かつ、
トリオキサンと、該トリオキサン 100質量部に対し 5. 0- 50. 0質量部の 1種以上の コモノマーとの共重合物である請求項 1に記載の樹脂材料の接着方法。
[化 2]
Figure imgf000012_0003
(式中、
Figure imgf000012_0004
R2はそれぞれ独立に、水素原子、アルキル基、アルキル基を有する有機 基、フエ二ル基、フエ二ル基を有する有機基を表す。 mは 1〜6の整数を表す。 )
[6] コモノマーが、 1 , 3—ジォキソランおよびその誘導体、 1 , 3—ジォキセパンおよび その誘導体、 1 , 3, 5—トリオキセパン及びその誘導体； 1 , 3, 6—トリオキソカンおよ びその誘導体、および単官能グリシジルエーテルからなる群から選ばれる少なくとも 1 種である請求項 4または 5に記載の樹脂材料の接着方法。
[7] 樹脂材料 (X)が、射出成形品、押出成形品、延伸成形品、またはそれらを 2次加工 した成形品であることを特徴とする請求項 1に記載の樹脂材料の接着方法。
[8] 樹脂材料 (X)の表面に、予めォキシメチレン系重合体組成物（B)を層状、又はドメ インとして存在させる請求項 1に記載の樹脂材料の接着方法。
[9] 請求項 1に記載の接着方法で得られる構造体。
PCT/JP2007/073344 2006-12-04 2007-12-03 オキシメチレン系重合体を含む樹脂材料の接着方法および構造体 Ceased WO2008069183A1 (ja)

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JPH0860125A (ja) 1994-08-25 1996-03-05 Polyplastics Co ポリアセタール樹脂用接着剤、接合方法およびその接合物
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KR20090094434A (ko) 2009-09-07
US20100041854A1 (en) 2010-02-18
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