JP6438787B2 - Mouthpiece laminate and mouthpiece - Google Patents

Description

  The present invention relates to a mouthpiece laminate and a mouthpiece.

  Medical mouthpieces are used for various purposes such as orthodontics, occlusal adjustment, improvement of bad biting habits, prevention of snoring, prevention of bruxism, and treatment of sleep apnea syndrome. For example, as an example used for orthodontics, RE-2011 / 090078 (Patent Document 1) describes (methyl) methacrylic resin having mechanical strength such as strength and hardness that can withstand long-term use. A composition is disclosed. Further, JP-A-2006-199622 (Patent Document 2) discloses a polymer composed of a repeating unit having an ester group that suppresses elution of an irritating substance often problematic in an acrylic resin composition, for example, A resin composition comprising a polyalkyl (meth) acrylate (A) and a vinyl ester monomer (B) is disclosed. However, in general, an acrylic resin composition is poor in shock absorption and may be damaged by an impact caused by dropping of an article, and there is room for improvement in terms of safety, handleability, and wearing feeling.

  Japanese Patent Application Laid-Open No. 5-23354 (Patent Document 3) discloses a crosslinked product obtained by crosslinking an ethylene-α olefin-diene copolymer. There was a problem of lowering.

  In addition, JP 2012-40136 A (Patent Document 4) manufactures a mouth guard (mainly a sports mouth guard) that has excellent shock absorption, is thinner than conventional ones, and can be reduced in weight and has a good wearing feeling. A mouth guard composition, a mouth guard sheet, and a mouth guard having such characteristics are disclosed. The mouth guard (mouthpiece) produced by the 4-methyl-1-pentene copolymer disclosed in Patent Document 4 and a composition containing the copolymer is flexible and lightweight, and has excellent impact absorption. Especially, when used as a sports mouth guard, the dentition and the head have a high protective effect. However, especially when used for medical purposes such as orthodontic, occlusal adjustment, improvement of occlusal habits, etc., not only adjustment of occlusal force and proper holding force for orthodontic, but also toothpaste and clenching There may be demands for seemingly contradictory functions, such as absorbing shock, and the development of a mouthpiece that satisfies these simultaneously is desired.

  To solve the problem of a mouthpiece made of a single layer, the inner layer of the mouthpiece that contacts the dentition is flexible and protects the dentition, and the outer layer is relatively hard and retains the shape of the mouthpiece. Therefore, a laminated mouthpiece having a function to do this is desired. For example, although there is a laminated mouthpiece of polyethylene terephthalate and thermoplastic polyurethane, further improvement is desired in impact absorption at the time of wearing and non-coloring property when exposed to food for a long time.

Table 2011/090078 JP 2006-199622 A JP-A-5-23354 JP 2012-40136 A

  The present invention solves the above problems, optimizes orthodontics and occlusal force, and is lightweight, hygienic and highly safe without applying excessive force to the teeth and dentition. The object is to provide a mouthpiece.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a laminated body for a mouthpiece having the following configuration, and have completed the present invention. The present invention relates to the following [1] to [6], for example.

[1] A first layer made of the composition (X) having a tensile modulus or bending elastic modulus at 23 ° C. of less than 800 MPa, and a thermoplastic resin having a tensile elastic modulus or bending elastic modulus at 23 ° C. of 800 MPa or more (C 2) and a second layer consisting of
The composition (X) comprises a structural unit (i) derived from 15 to 87 mol% 4-methyl-1-pentene and a structural unit (ii) derived from 13 to 85 mol% propylene (provided that 4-methyl-1-pentene / propylene copolymer (A) consisting of unit (i) and structural unit (ii) of 100 mol%), and thermoplastic resin And 50 to 0 parts by weight of at least one polymer (B) selected from the group consisting of rubber and rubber (provided that the total amount of the copolymer (A) and the polymer (B) is 100 parts by weight). Contains a laminated body for mouthpiece.

  [2] The laminate for a mouthpiece according to [1], wherein the thermoplastic resin (C) is at least one selected from the group consisting of polypropylene and polyethylene terephthalate.

[3] The laminate for a mouthpiece according to [1] or [2], wherein the thickness is 0.3 mm to 5.0 mm.
[4] A mouthpiece comprising the laminate for a mouthpiece according to any one of [1] to [3].
[5] The mouthpiece according to [4], wherein an inner layer in contact with the dentition of the mouthpiece is the first layer, and an outer layer is the second layer.
[6] The method for manufacturing a mouthpiece according to [4] or [5], wherein the mouthpiece laminate is heated until softened, and the mouthpiece is manufactured along a dentition model or a jaw model.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in shock absorption, a feeling of mounting | wearing, and the laminated body for mouthpieces for carrying out shape supplement maintenance for a long-term use, and the mouthpiece which has such a characteristic are provided.

Hereinafter, the laminate for a mouthpiece and the mouthpiece of the present invention will be described in more detail.
The laminate for a mouthpiece of the present invention has a first layer made of the composition (X) having a tensile modulus or bending elastic modulus at 23 ° C. of less than 800 MPa, and a tensile elastic modulus or bending elastic modulus at 23 ° C. of 800 MPa or more. It consists of at least two layers with the 2nd layer which consists of a thermoplastic resin (C) which is.

[First layer]
The 1st layer which comprises the laminated body for mouthpieces and mouthpiece of this invention consists of a composition (X) whose tensile elastic modulus measured by JISK7162 or bending elastic modulus measured by JISK7171 is less than 800 MPa. . A tensile elasticity modulus and a bending elasticity modulus are the values at the time of measuring with the conditions and methods shown in an Example based on each JIS specification.

  The composition (X) used for the first layer comprises a structural unit (i) derived from 15 to 87 mol% of 4-methyl-1-pentene and a structural unit (ii) derived from 13 to 85 mol% of propylene. ) (Provided that the total of the structural unit (i) and the structural unit (ii) is 100 mol%). 4-methyl-1-pentene / propylene copolymer (A) 50 to 100 parts by weight, And 50 to 0 parts by weight of at least one polymer (B) selected from the group consisting of a thermoplastic resin and rubber (however, the total amount of the copolymer (A) and the polymer (B) is 100 parts by weight) And). An embodiment in which the amount of the polymer (B) is 0 part by weight is also expressed as a “composition” for convenience.

<4-Methyl-1-pentene / propylene copolymer (A)>
(composition)
The proportion of the structural unit (i) in the 4-methyl-1-pentene / propylene copolymer (A) (hereinafter also simply referred to as “copolymer (A)”) is 15 to 87 mol%, preferably It is 20-87 mol%, More preferably, it is 65-87 mol%, and the ratio of structural unit (ii) is 13-85 mol%, Preferably it is 13-80 mol%, More preferably, it is 13-35 mol% .

  If the proportion of the structural unit (i) is less than 15 mol%, the shock absorption, flexibility and lightness of the mouthpiece are impaired, and if it is more than 87 mol%, the shock absorption of the mouthpiece is lost. And the flexibility and flexibility are impaired.

  The copolymer (A) may contain a structural unit derived from another monomer as long as it is a small amount (for example, 10 mol% or less) that does not impair the object of the present invention. Specific examples of other monomers are preferably ethylene, 1-butene, 1-hexene, 1-octene and the like.

(Physical properties)
The intrinsic viscosity [η] of the copolymer (A) in decalin at 135 ° C. is preferably 0.01 to 5.0 (dL / g), more preferably 0.05 to 4.0 (dL / g). g), more preferably 0.1 to 3.0 (dL / g), and particularly preferably 0.5 to 2.5 (dL / g). As described later, when hydrogen is used together during polymerization, the molecular weight can be controlled, and the intrinsic viscosity [η] can be adjusted by freely obtaining from a low molecular weight body to a high molecular weight body.

  The weight average molecular weight (Mw) of the copolymer (A) measured by gel permeation chromatography (GPC) is preferably 1,000 to 5,000,000, more preferably 1, in terms of polystyrene. 000 to 2,500,000.

  The ratio (molecular weight distribution; Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the copolymer (A) is preferably 1. It is 0.0-3.5, More preferably, it is 1.2-3.0, More preferably, it is 1.5-2.5.

The copolymer (A) having an Mw / Mn value within the above range is advantageous in producing a mouth guard having excellent mechanical properties and wear resistance with excellent moldability, and has an industrial value. taller than.
If a catalyst described later is used, a copolymer (A) having a value of Mw / Mn within the above range within the range of the intrinsic viscosity [η] or the weight average molecular weight (Mw) described above can be obtained. . The values of Mw / Mn and Mw are values measured by the method employed in the examples described later.

  The amount of copolymer (A) extracted with methyl acetate is preferably 0 to 1.5% by weight, more preferably 0 to 1.0% by weight, still more preferably 0 to 0.8% by weight, particularly preferably. 0 to 0.5% by weight. The amount of methyl acetate extracted becomes an index of stickiness during molding. When this value is large, the obtained polymer has a large composition distribution and contains a low molecular weight polymer, causing problems during molding. When the methyl acetate extraction amount is within the above range, there is no problem due to stickiness during molding. In addition, by using the catalyst described later, a copolymer (A) with a low stereoregularity and atactic component can be synthesized, and by molding the obtained polymer, a mouthpiece having no stickiness and excellent hygiene can be obtained. It is done.

The density of the copolymer (A) (measured by ASTM D 1505) is preferably 880 to 810 kg / m ³ , more preferably 860 to 820 kg / m ³ , and still more preferably 855 to 830 kg / m ³ .

The density can be changed by the comonomer composition ratio of the copolymer (A), and the copolymer (A) within the above range is advantageous in producing a lightweight mouthpiece.
The melting point [Tm] of the copolymer (A) measured by a differential scanning calorimeter (DSC) is preferably less than 110 ° C. or not recognized. The melting point can be changed by the comonomer composition ratio of the 4-methyl-1-pentene / propylene copolymer (A), and the copolymer (A) within the above range is used for producing a flexible mouthpiece. Is advantageous.

  The maximum value of the loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s in the temperature range of −40 ° C. to + 180 ° C. of the copolymer (A) is preferably 0.1 to 10, More preferably, it is 0.4-8.0, More preferably, it is 0.6-6.0, Most preferably, it is 1.5-5.0, Most preferably, it is 2.0-4.0. The temperature at which the value of tan δ is maximized is preferably −50 ° C. to 100 ° C., more preferably −30 ° C. to 50 ° C., further preferably −10 ° C. to 40 ° C., and particularly preferably 0 ° C. to 40 ° C. It is in the range of ° C. The maximum value of tan δ can be controlled by the comonomer composition ratio of the copolymer (A). For example, the 4-methyl-1-pentene content in the copolymer (A) is 20 to 72 mol%. , Tan δ can be within the above range. The measurement conditions for dynamic viscoelasticity are as follows.

  A press sheet having a thickness of 3 mm was prepared, and a strip of 45 mm × 10 mm × 3 mm necessary for dynamic viscoelasticity measurement was cut out. The temperature dependence of dynamic viscoelasticity from −40 to 180 ° C. was measured at a frequency of 10 rad / s using MTON 301 manufactured by ANTONPaar, and the loss tangent (tan δ) due to the glass transition temperature was the peak value (maximum value). ) (Hereinafter also referred to as “peak temperature”), and the value of loss tangent (tan δ) at that time.

The copolymer (A) has a rebound elastic modulus (%) defined by the following formula at 0 to 25%, preferably 0 to 20%, more preferably at 40 ° C, which is a temperature condition assuming the oral cavity. 0 to 10%.
Rebound resilience (%) = (Rebound height) (mm) / 460 × 100
The rebound resilience can be controlled by the comonomer composition ratio of the copolymer (A). For example, the rebound resilience is within the above range by setting the 4-methyl-1-pentene content to 20 to 65 mol%. Can do.

(Production method)
For the production of the copolymer (A), a conventionally known catalyst such as a magnesium-supported titanium catalyst, WO 01/53369 pamphlet, WO 01/27124 pamphlet, Japanese Patent Laid-Open No. 3-193796 or The metallocene catalyst described in Kaihei 02-41303 is preferably used, and more preferably, an olefin polymerization catalyst containing a metallocene compound represented by the following general formula (1) or (2) is preferably used. .

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are hydrogen, hydrocarbon. Group and silicon-containing hydrocarbon group, which may be the same or different, and adjacent substituents from R ¹ to R ⁴ may be bonded to each other to form a ring, from R ⁵ to R ¹² Adjacent substituents may be bonded to each other to form a ring,
A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and A is two or more rings including a ring formed with Y May contain structure,
M is a metal selected from Group 4 of the periodic table,
Y is carbon or silicon;
Q is selected from the same or different combinations from halogen, hydrocarbon groups, and anionic ligands or neutral ligands capable of coordinating with lone pairs;
j is an integer of 1-4.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ^{13 in the} general formula (1) or (2) R ¹⁴ is selected from hydrogen, a hydrocarbon group and a silicon-containing hydrocarbon group, and may be the same or different.

  The hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. Yes, it may contain one or more ring structures. Moreover, a part or all of hydrogen of the hydrocarbon group may be substituted with a functional group such as a hydroxyl group, an amino group, a halogen group, or a fluorine-containing hydrocarbon group. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, and 1-ethyl-1. -Methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl -1-cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, biphenyl, Naphthyl, tolyl, chlorophenyl, chlorobipheny , Chloronaphthyl, and the like.

  The silicon-containing hydrocarbon group is preferably an alkylsilyl group or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl and the like. Is mentioned.

Adjacent substituents from R ⁵ to R ¹² on the fluorene ring may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like.

The substituents R ⁵ to R ¹² on the fluorene ring are symmetrical from the viewpoint of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ , and R ⁸ = R ^9. And the fluorene ring is more preferably unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Wherein the 3-position on the fluorene ring, 6-position, 2-position, 7-position corresponds to the ^{R 7, R 10, R 6} , R 11 , respectively.

R ¹³ and R ^{14 in} the general formula (1) are selected from hydrogen and a hydrocarbon group, and may be the same or different. Specific examples of preferred hydrocarbon groups include the same as those described above.

Y is carbon or silicon. In the case of the general formula (1), R ¹³ and R ¹⁴ are bonded to Y to form a substituted methylene group or a substituted silylene group as a bridging part. Preferred examples include methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, fluoromethylphenylmethylene, chloromethylphenylmethylene, diphenylmethylene, dichlorophenylmethylene, difluorophenylmethylene. Methylnaphthylmethylene, dibiphenylmethylene, di-p-methylphenylmethylene, methyl-p-methylphenylmethylene, ethyl-p-methylphenylmethylene, dinaphthylmethylene or dimethylsilylene, diisopropylsilylene, methyl-tert-butylsilylene, dicyclohexyl Silylene, methylcyclohexylsilylene, methylphenylsilylene, fluoromethyl Enirushiriren, chloromethyl silylene, diphenyl silylene, mention may be made of di-p- methylphenyl silylene, methyl -p- methylphenyl silylene, ethyl -p- methylphenyl silylene, methyl naphthyl silylene, a dinaphthyl silylene like.

  In the case of the general formula (2), Y is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and a cycloalkylidene group or It constitutes a cyclomethylenesilylene group and the like. Preferred examples include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanidene. Examples include lidene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and the like.

M in the general formulas (1) and (2) is a metal selected from Group 4 of the periodic table, and examples of M include titanium, zirconium, and hafnium.
Q is selected from the same or different combinations from halogen, a hydrocarbon group having 1 to 20 carbon atoms, and an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair. Specific examples of the halogen include fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, and tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, Q may be the same or different combinations, but at least one is preferably a halogen or an alkyl group.

  Specific examples of the metallocene compound in the present invention include compounds exemplified in WO 01/27124, WO 2006/025540, or WO 2007/308607. In particular, this does not limit the scope of the present invention.

When a metallocene compound is used for the production of the copolymer (A), the catalyst component is
(A) a metallocene compound (for example, a metallocene compound represented by the above general formula (1) or (2));
(B) (b-1) an organoaluminum oxy compound,
(B-2) a compound that reacts with the metallocene compound (A) to form an ion pair, and (b-3) at least one compound selected from organoaluminum compounds;
If necessary,
(C) It is comprised from a particulate carrier. As a production method, for example, the method described in International Publication No. 01/27124 pamphlet can be employed.

  Further, it reacts with an organoaluminum oxy compound (b-1) (hereinafter also referred to as “component (b-1)”) and a metallocene compound (a) (hereinafter also referred to as “component (a)”) to form an ion pair. Specifics of compound to be formed (hereinafter also referred to as “component (b-2)”), organoaluminum compound (b-3) (hereinafter also referred to as “component (b-3)”), and particulate carrier (c) Examples include those compounds or carriers conventionally known in the field of olefin polymerization, such as the specific examples described in WO 01/27124.

In the production of the copolymer (A), the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.
In the liquid phase polymerization method, an inert hydrocarbon solvent may be used. Specific examples of the inert hydrocarbon include aliphatic carbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Hydrogen; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogens such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane And hydrocarbons, and mixtures thereof.

Bulk polymerization using 4-methyl-1-pentene and propylene itself as a solvent can also be carried out.
Further, 4-methyl-1-pentene / propylene copolymer having a controlled composition distribution was obtained by performing stepwise polymerization of 4-methyl-1-pentene and copolymerization of 4-methyl-1-pentene and propylene. It is also possible to obtain a polymer (A).

In carrying out the polymerization, the component (a) is usually 10 ⁻⁸ to 10 ⁻² mol, preferably 10 ⁻⁷ to 10 ⁻³ mol, in terms of group 4 metal atom in the periodic table, per liter of reaction volume. Used in various amounts. In the component (b-1), the molar ratio [(b-1) / M] of the component (b-1) and the transition metal atom (M) in the component (a) is usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. In the component (b-2), the molar ratio [(b-2) / M] of the component (b-2) and the transition metal atom (M) in the component (a) is usually 1 to 10, preferably 1. Used in an amount such that it is ˜5. Component (b-3) has a molar ratio [(b-2) / M] of component (b-3) to transition metal atom (M) in component (a) of usually 10 to 5000, preferably 20 It is used in an amount such that it is ˜2000.

The polymerization temperature is usually in the range of −50 to 200 ° C., preferably 0 to 100 ° C., more preferably 20 to 100 ° C.
The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  Hydrogen may be added for the purpose of controlling the molecular weight and polymerization activity of the produced polymer during the polymerization, and the amount is suitably about 0.001 to 100 NL per 1 kg of the total of 4-methyl-1-pentene and propylene.

<Polymer (B)>
The polymer (B) is not particularly limited, and for example, a thermoplastic polyolefin resin (excluding the copolymer (A)), a thermoplastic polyamide resin, a thermoplastic polyester resin, a thermoplastic vinyl aromatic. Resin, thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; ethylene / vinyl acetate copolymer; ethylene / methacrylic acid acrylate copolymer; ionomer; ethylene / vinyl alcohol copolymer; Polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide polyimide, polyarylate, polysulfone, polyethersulfone, rosin resin, terpene resin, petroleum resin, copolymer rubber, and the like.

  Specific examples of the thermoplastic polyolefin resin (excluding the copolymer (A)) include low density, medium density, high density polyethylene, high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, Poly 1-butene, poly 4-methyl-1-pentene, poly 3-methyl-1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin copolymer Examples thereof include a coalescence, a cyclic olefin copolymer, and a chlorinated polyolefin.

  Specific examples of the thermoplastic polyamide-based resin include aliphatic polyamides (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612) and the like.

Specific examples of the thermoplastic polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyester elastomer.
Specific examples of the thermoplastic vinyl aromatic resin include polystyrene, ABS resin, AS resin, styrene elastomer (styrene / butadiene / styrene block polymer, styrene / isoprene / styrene block polymer, styrene / isobutylene / styrene block polymer, And the aforementioned hydrogenated product).

  Examples of the rosin resin include natural rosin, polymerized rosin, modified rosin and rosin derivatives modified with maleic acid, fumaric acid, (meth) acrylic acid, and the like. Examples of the rosin derivative include the above-mentioned natural rosin, polymerized rosin or esterified product of modified rosin, phenol-modified product and esterified product thereof. Furthermore, these hydrogenated substances can also be mentioned.

  Examples of the terpene resin include resins composed of α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, terpene aldehyde, etc., and α-pinene, β-pinene, limonene, dipentene, etc. An aromatic modified terpene resin obtained by polymerizing aromatic monomers such as α-methylstyrene and isopropenyltoluene. Moreover, these hydrogenated substances can also be mentioned.

  Examples of the petroleum resin include an aliphatic petroleum resin mainly containing a C5 fraction of tar naphtha, an aromatic petroleum resin mainly containing a C9 fraction and a copolymer petroleum resin thereof. That is, C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) And styrene / α-methylstyrene copolymer petroleum resin, α-methylstyrene polymer petroleum resin, isopropenyltoluene polymer petroleum resin, and the like. Coumarone indene resins containing styrenes, indenes, coumarone, other dicyclopentadiene, alkylphenol resins represented by condensates of p-tertiarybutylphenol and acetylene, o-xylene, p-xylene or Examples thereof include xylene-based resins obtained by reacting m-xylene with formalin.

  One or more resins selected from the group consisting of rosin resins, terpene resins, and petroleum resins are preferably hydrogenated derivatives because they are excellent in weather resistance and discoloration resistance. The softening point of the resin by the ring and ball method is preferably in the range of 40 to 180 ° C. The number average molecular weight (Mn) molecular weight measured by GPC of the resin is preferably in the range of about 100 to 10,000.

A commercially available product may be used as one or more resins selected from the group consisting of rosin resins, terpene resins and petroleum resins.
Specific examples of the copolymer rubber include ethylene / α-olefin / diene copolymer, propylene / α-olefin / diene copolymer, 1-butene / α-olefin / diene copolymer, polybutadiene rubber, Examples include isoprene rubber, neoprene rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, natural rubber, and silicone rubber.

  Among these, low density, medium density, high density polyethylene, high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl-1-pentene, poly 3-methyl-1 -Butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin copolymer, polystyrene, styrene elastomer, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid Preferred forms of acrylate copolymer, ionomer, fluorine resin, rosin resin, terpene resin and petroleum resin are isotactic polypropylene, poly 1-butene, poly 4-methyl-1-pentene, ethylene / α-olefin. Copolymer, propylene / α-olefin Copolymer, 1-butene / α-olefin copolymer, ethylene / vinyl acetate copolymer, styrene elastomer, rosin resin, terpene resin, petroleum resin, ethylene / α-olefin / diene copolymer , Propylene / α-olefin / diene copolymer, 1-butene / α-olefin / diene copolymer, polybutadiene rubber, polyisoprene rubber, neoprene rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, and silicone rubber are preferable.

<Softener>
In the composition (X), a softener may be blended as necessary within a range not impairing the object of the present invention. As the softener, a conventionally known softener that is usually used can be used. Specifically, petroleum-based substances such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt and petroleum jelly; coal tars such as coal tar and coal tar pitch; castor oil, linseed oil, Fat oils such as rapeseed oil, soybean oil and coconut oil; waxes such as tall oil, beeswax, carnauba wax and lanolin; ricinoleic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, montanic acid, oleic acid and elca Fatty acids such as acids or metal salts thereof; synthetic polymers such as petroleum resins, coumarone indene resins and atactic polypropylene; ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; other microcrystals WAX, and liquid polybutadiene or its modified product or hydrogenated product; and liquid Thiokol and the like.

<Other additives>
The composition (X) has various weather resistance stabilizers, heat resistance stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, anti-slip agents, anti-blocking agents, anti-fogging agents within the range not impairing the object of the present invention. Agent, nucleating agent, lubricant, pigment, dye, anti-aging agent, hydrochloric acid absorbent, inorganic or organic filler, organic or inorganic foaming agent, crosslinking agent, co-crosslinking agent, crosslinking aid, adhesive, flame retardant Such additives may be blended as necessary.

  Specific examples of additives include phenolic stabilizers, 2,6-di-t-butyl-p-cresol, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ] Methane, 4,4'-butylidenebis (6-t-butyl-m-cresol), tocopherols, ascorbic acid, dilauryl thiodipropionate, phosphoric acid stabilizer, fatty acid monoglyceride, N, N- [bis- 2-hydroxyethyl] alkylamine, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, calcium stearate, magnesium oxide, magnesium hydroxide, alumina, hydroxylation Aluminum, silica, clay, gypsum, glass fiber, titania, calcium carbonate, carbon black, etc. It is done.

<Composition (X)>
The composition (X) contains 50 to 100 parts by weight of the copolymer (A) and 50 to 0 parts by weight of the polymer (B) (provided that the copolymer (A) and the polymer (B) From the viewpoint of impact absorption of the mouthpiece, the lower limit of the copolymer (A) is preferably 52 parts by weight, more preferably 55 parts by weight, and particularly preferably Is 60 parts by weight, and the upper limit of the copolymer (A) is preferably 98 parts by weight, more preferably 95 parts by weight, particularly preferably from the viewpoint of shock absorption, flexibility and lightness of the mouthpiece. Is 90 parts by weight.

  The composition (X) can be prepared by mixing the copolymer (A) and the polymer (B) and optionally the additives. As a manufacturing method, a conventionally known mixing method, for example, a method of mixing with a plast mill, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, a kneader ruder or the like, or after mixing, a single screw extruder, a twin screw extruder, a kneader It can be produced by adopting a method of granulating or pulverizing after melt-kneading with a Banbury mixer or the like.

The composition (X) preferably has the following physical properties.
(A): Shore A hardness value (details such as measurement conditions are as described in the column of Examples described later) is 5 to 90, preferably 10 to 80, more preferably 15 to 70, Especially preferably, it is 15-65.

  The Shore A hardness value of the composition (X) can be arbitrarily changed depending on the comonomer composition ratio of the copolymer (A) or the mixing ratio of the components in the composition (X). When it is within the range, the mouthpiece is excellent in flexibility.

  (B): The maximum value of loss tangent tan δ obtained by dynamic viscoelasticity measurement at a frequency of 10 rad / s in the temperature range of −40 ° C. to + 180 ° C. is 0.1 to 10, preferably 0.4 to 8. More preferably, it is 0.6-6, More preferably, it is 0.8-4. The temperature at which the value of tan δ is maximized is in the range of −50 ° C. to 100 ° C., preferably −30 ° C. to 50 ° C., more preferably −10 ° C. to 40 ° C. If the maximum value of tan δ is within these ranges, the mouthpiece can exhibit excellent shock absorption. The maximum value of tan δ can be controlled by the comonomer composition ratio of the copolymer (A) or the mixing ratio of the copolymer (A) and the polymer (B) in the composition (X). By setting the methyl-1-pentene content to 20 to 65 mol%, the maximum value of tan δ can be within the above range. The measurement conditions for dynamic viscoelasticity are as follows.

  A press sheet having a thickness of 3 mm was prepared, and a strip of 45 mm × 10 mm × 3 mm necessary for dynamic viscoelasticity measurement was cut out. The temperature dependence of dynamic viscoelasticity from −40 to 180 ° C. was measured at a frequency of 10 rad / s using MTON 301 manufactured by ANTONPaar, and the loss tangent (tan δ) due to the glass transition temperature was the peak value (maximum value). ) (Hereinafter also referred to as “peak temperature”), and the value of loss tangent (tan δ) at that time.

(C): Rebound resilience (%) defined by the following formula (details of measurement conditions and the like are as described in the column of Examples described later) are 0 to 30% at room temperature (23 ° C.). It is preferably 0 to 20%, more preferably 0 to 15%. At 40 ° C., which is a temperature condition assuming the oral cavity, 0 to 30%, preferably 0 to 25%, more preferably 0 to 20% It is.
Rebound resilience (%) = (Rebound height) (mm) / 460 × 100
The rebound resilience can be controlled by the comonomer composition ratio of the copolymer (A) or the mixing ratio of the copolymer (A) and the polymer (B) in the composition (X). By setting the methyl-1-pentene content to 20 to 65 mol%, the rebound resilience can be within the above range.

<Graft modification>
As long as the object of the present invention is not impaired, part or all of the copolymer (A) may be graft-modified, and part or all of the polymer (B) may be graft-modified. . Examples of the polar compound used for graft modification and the graft modification method include conventionally known compounds and methods. For example, the compounds and methods described in JP-A-2008-127440 can be employed.

The graft amount of the graft modified product is usually 0.1 to 40% by weight, preferably 0.2 to 30% by weight, and more preferably 0.2 to 20% by weight.
When the copolymer (A) or the polymer (B) is graft-modified, it is advantageous in terms of compatibility or adhesiveness of the composition.

<Crosslinking>
At least a part or all of the composition (X) may be crosslinked with a crosslinking agent.

  There is no restriction | limiting in particular as a crosslinking agent, Sulfur, an organic peroxide, and a SiH group containing compound are mentioned. When using sulfur, the amount thereof is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight in total of the copolymer (A) and the polymer (B) in the composition (X). It is. When using an organic peroxide, the amount is preferably 0.05 to 100 parts by weight with respect to a total of 100 parts by weight of the copolymer (A) and the polymer (B) in the composition (X). 15 parts by weight.

  When the SiH group-containing compound is used, the amount thereof is preferably 0.1% relative to 100 parts by weight of the total of the copolymer (A) and the polymer (B) in the composition (X). It is 2-20 weight part, More preferably, it is 0.5-10 weight part, More preferably, it is 0.5-5 weight part. When using an SiH group-containing compound, a silane coupling agent and / or a reaction inhibitor may be added as a catalyst and optional components.

[Second layer]
The second layer constituting the mouthpiece laminate and the mouthpiece of the present invention is made of a thermoplastic resin (C) having a tensile elastic modulus measured by JIS K7162 or a bending elastic modulus measured by JIS K7171 of 800 MPa or more. Become.

<Thermoplastic resin (C)>
The thermoplastic resin (C) is not particularly limited as long as the tensile modulus measured according to JIS K7162 or the flexural modulus measured according to JIS K7171 is 800 MPa or more. For example, a polyolefin resin, a polyester resin, Examples thereof include polystyrene resins and acrylic resins.

Specifically, polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS), and polymethyl methacrylate (PMMA) are preferably used, and PP and PET-G are particularly preferably used. Even when the second layer is such a resin composition, one not included in the range of the tensile elastic modulus of the first layer is used. Examples of commercially available products of these resins, for example, (manufactured by (Corporation) Prime Polymer) Prime Polypro [trademark], Novatec ^TM (manufactured by Japan Polypropylene Corporation), clappet (produced by Kuraray Co., Ltd.), Unipet (Japan Uni Examples include thermoplastic resins manufactured and sold under trade names such as Pet Co., Ltd., Novapex [registered trademark] (Mitsubishi Chemical Co., Ltd.), and SKYGREEN PETG (Korea SK Chemical).

[Laminate for mouthpiece]
The laminated body for mouthpiece of the present invention is obtained by laminating at least the first layer and the second layer described above. The first layer and the second layer described above are formed by extrusion molding, calendar molding, press molding, injection molding, vacuum molding, pressure molding, vacuum pressure molding, etc., respectively, from the above-described composition (X) and thermoplastic resin (C). It is formed by processing into a sheet by any molding method.

  In order to improve the adhesion between the first layer and the second layer, these layers may be laminated via adhesive layers using various known adhesives, such as adhesives, pressure-sensitive adhesives, A photocurable adhesive and a hot melt adhesive can be used. Such adhesives include acrylic adhesives, urethane adhesives, epoxy adhesives, polyester adhesives, polyvinyl alcohol adhesives, polyolefin adhesives, modified polyolefin adhesives, polyvinyl alkyl ether adhesives, rubber adhesives, vinyl chloride / Vinyl acetate adhesive, styrene / butadiene / styrene copolymer (SBS copolymer) Adhesive, hydrogenated product (SEBS copolymer) adhesive, ethylene / vinyl acetate copolymer, ethylene-styrene copolymer, etc. Ethylene adhesive, ethylene / methyl methacrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / ethyl acrylate copolymer and other acrylic ester adhesives, etc. If the adhesiveness, transparency, and workability are good, It is not limited.

  The thickness of the laminated body for mouthpiece of the present invention is required to have a strength capable of protecting the dentition and not bad in wearing feeling, preferably 0.3 mm to 5.0 mm, more preferably 0.4 mm to 4 mm. 0.5 mm, more preferably 0.5 mm to 4.0 mm.

[Mouthpiece]
The mouthpiece of this invention consists of the laminated body for mouthpieces of this invention.
The mouthpiece of the present invention is manufactured in the same manner as the conventional mouthpiece except that the material is a laminate for the mouthpiece of the present invention, for example, in WO 2002/98521, JP 2010-131181. It can be produced by the method described. More specifically, the mouthpiece laminate is heated until softened, and the mouthpiece is manufactured along the dentition model or jaw model, the concave mold using the dentition model or jaw model. The mouthpiece can be manufactured by, for example, a method of manufacturing the mouthpiece by injecting the laminated body for the mouthpiece therein.

  In the mouthpiece of the present invention, it is preferable that the inner layer in contact with the dentition is the first layer and the outer layer is the second layer. The dentition surface (inner side) of the mouthpiece of the present invention is composed of the first layer described above, and thus has the following advantages.

・ Because the material has high shock absorption, it is not only excellent in wearing feeling even if it is thinner than conventional products, but also excellent in shock absorption.
-Since the rebound resilience of the material is low, it has an excellent fit, especially when it is tightly tightened.
-Since the Shore A hardness of the material is low, it follows the unevenness of the teeth and is excellent in wearing comfort. In particular, when a mouthpiece at room temperature is bitten in the mouth, the shape following property (stress relaxation) at the mouth temperature is excellent.
-Light weight due to low material density.
-The material has high wear resistance and excellent durability.
・ There is no odor unlike mouthpiece made of styrene elastomer.
-Since the softening temperature is low, it is excellent in moldability compared to EVA mouthpieces.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples.
[Measurement conditions]
The measurement conditions of the physical properties in the examples are as follows.

〔composition〕
The 4-methyl-1-pentene and propylene contents in the polymer were measured by ¹³ C-NMR with the following apparatus and conditions. Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of orthodichlorobenzene / heavy benzene (80/20% by volume) as a solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120 ° C., observation nucleus ¹³ C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45 ° pulse), repetition time is 5.5 seconds, integration number is 10,000 times or more, 27.50 ppm as standard for chemical shift Measured as a value.

〔density〕
The density of the polymer was calculated from the weight of each sample measured in water and in air using ALFA MIRAGE electronic hydrometer MD-300S according to ASTM D 1505 (substitution in water).

[Intrinsic viscosity]
The intrinsic viscosity [η] of the polymer was measured at 135 ° C. using a decalin solvent.
[Molecular weight (Mw, Mn) / Molecular weight distribution (Mw / Mn)]
The molecular weight of the polymer is a liquid chromatograph: Waters ALC / GPC 150-C plus type (with suggested refractometer detector), and Tosoh Corporation GMH6-HT × 2 and GMH6-HTL × 2 as columns. Were connected in series, and o-dichlorobenzene was used as a mobile phase medium, and the flow rate was 1.0 ml / min and measurement was performed at 140 ° C.

  Mw / Mn value, Mw value, and Mn value were calculated by analyzing the obtained chromatogram by a known method using a calibration curve using a standard polystyrene sample. The measurement time per sample was 60 minutes.

[Methods for producing various measurement press sheets]
Each composition of the example and the comparative example was formed into a sheet at a pressure of 10 MPa using a hydraulic hot press machine manufactured by Shindo Metal Industry Co., Ltd. set at 190 ° C. In the case of a 0.5-2 mm thick sheet (200 × 200 × 0.5-2 mm), the remaining heat is about 5-7 minutes, and after pressurizing at 10 MPa for 1-2 minutes, another Kamito set at 20 ° C. Using a hydraulic hot press machine manufactured by Metal Industry Co., Ltd., the sample was compressed at 10 MPa and cooled for about 5 minutes to prepare a measurement sample. A 5 mm thick brass plate was used as the hot plate. In the case of a laminated body, the sheet was heat-sealed again by the above method to produce a laminated sheet having a thickness of 1 to 2 mm, and these samples were used for various physical property evaluation samples.

[Mouthpiece moldability]
Each press sheet having a thickness of 1 mm obtained above is subjected to a vacuum forming machine (airbag XQ, manufactured by Yamahachi Teigaku Kogyo Co., Ltd.) with the flexible layer (first layer) of the laminated sheet on the dentition surface. A mouthpiece that fits the tooth model was prepared. The formability was evaluated by measuring the temperature (° C.) when the press sheet was overheated and melted and dropped from the set position to 1.5 cm by gravity and the time (sec) after the start of heating. In addition, regarding the appearance of the mouthpiece after vacuum forming, there is no stickiness, there are no bubbles or kinks (whitening), and it fits the jaw model and does not float against the dentition, Sensory evaluation was performed.

[Shore A hardness]
Measurement was performed in accordance with JIS K6253.
(Flexural modulus)
In accordance with JIS K7171, a 2 mm-thick press sheet or a laminated sheet obtained by the above method was used at a speed of 1 mm / min in an atmosphere at 23 ° C.
[Tensile modulus]
In accordance with JIS K7162, it was carried out at a speed of 200 mm / min in an atmosphere of 23 ° C. using a 2 mm thick press sheet obtained by the above method.
[Rebound resilience]
In accordance with JIS K6400, the bounce height L (mm) when a 16.310 g rigid ball is dropped from a 460 mm height onto a 2 mm thick press sheet or laminated sheet is measured and defined by the following formula: The impact resilience was evaluated.
Rebound resilience (%) = L (mm) / 460 × 100

[Compressive stress relaxation rate]
In the measurement of the compression stress relaxation rate, a press sheet having a thickness of 2 mm was used. In the stacking direction of the measurement sample, a compression jig having a tip diameter of 5 mm used for a bending test or the like was pushed at 23 ° C. or 37 ° C. at a speed of 10 mm / min to compress the measurement sample. When the load reaches 500 N (approximately 50 kgf) (hereinafter referred to as “maximum load”), which corresponds to the force of an adult male biting the back teeth, further compression is stopped, and the load after being left for 5 minutes (relaxed load) ) And the ratio (post-relaxation load / maximum load) was defined as the compression stress relaxation rate (%). The compressive stress relaxation rate is considered to be temperature dependent depending on the material. The lower the compressive stress relaxation rate at room temperature, the better the shape followability when starting to bite the mouthpiece and the faster the fitting to the dentition. Further, it is desirable that the compressive stress relaxation rate at 37 ° C. (in the mouth environment) is not too low for maintaining the shape of the mouthpiece.

[Water absorption rate]
Based on ASTM D570-98, the water absorption rate (%) after a 24-hour immersion of a 1 mm-thick press sheet or laminated sheet in a 37 ° C. water bath was determined.

[Haze]
Based on JIS K7136, the haze of a 1 mm-thick press sheet or laminated sheet was measured with a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[Colorability]
The press sheet or laminated sheet having a thickness of 1 mm obtained above was immersed in a coffee liquid adjusted to 1.4 wt% of commercially available instant coffee and held at 37 ° C. for 24 hours. The color difference (ΔE) measurement was performed using Color Mode CC-i (manufactured by Suga Test Instruments Co., Ltd.) and the reflection mode for the colorability of the press sheet taken out after 24 hours.

[Evaluation of mouthpiece wearing feeling]
About the feeling of mounting | wearing of the mouthpiece obtained using the vacuum forming machine above, superiority and inferiority with respect to a commercially available soft type mouthpiece were performed by sensory evaluation.

<Synthesis Example 1>
A SUS autoclave with a stirring blade having a capacity of 1.5 liters sufficiently purged with nitrogen was charged with 300 ml of normal hexane at 23 ° C. (dried in a dry nitrogen atmosphere and activated alumina) and 450 ml of 4-methyl-1-pentene. . The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.

  Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure was 0.40 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance, diphenylmethylene (1-ethyl-3-tert-butyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium in terms of Al Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.01 mmol of dichloride into the autoclave with nitrogen. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

  The obtained powdered polymer containing the solvent was dried at 100 ° C. under reduced pressure for 12 hours. The obtained polymer was 36.9 g, and the 4-methyl-1-pentene content in the polymer was 72.5 mol% and the propylene content was 27.5 mol%. Table 1 shows the measurement results of various physical properties.

[Example 1]
Using the 4-methyl-1-pentene / propylene copolymer (A) obtained in Synthesis Example 1, press sheets having a thickness of 0.5 mm and a thickness of 1 mm were prepared as described above. Similarly, 0.5 mm and 1 mm thick press sheets of syndiotactic polypropylene obtained by the method described in WO2006 / 123759 were prepared. These two types of press sheets were further heat-sealed by the above-described method to produce laminated sheets having a total thickness of 1 mm and 2 mm, respectively, and each physical property was evaluated. The results are shown in Table 2. The tensile elastic modulus of only the second layer was 858 MPa. A laminated mouthpiece having excellent moldability was obtained, and a sheet having a low impact resilience, excellent dentition surface mounting feeling, and excellent appearance such as transparency and non-coloring properties was obtained. Moreover, when the mouthpiece was attached, the fit was superior to that of a commercially available product.

[Example 2]
Except for changing the second layer to a commercially available isotactic polypropylene prime polypro [registered trademark] F327 (manufactured by Prime Polymer Co., Ltd.), press sheets of 0.5 mm and 1 mm thickness were used in the same manner as in Example 1. Produced. These two types of press sheets were further heat-sealed by the above-described method to produce laminated sheets having a total thickness of 1 mm and 2 mm, respectively, and each physical property was evaluated. The results are shown in Table 2. Note that the tensile elastic modulus of only the second layer was 850 MPa. A laminated mouthpiece having excellent moldability was obtained, and a sheet having a low impact resilience, excellent dentition surface mounting feeling, and excellent appearance such as transparency and non-coloring properties was obtained. Moreover, when the mouthpiece was attached, the fit was superior to that of the commercially available product or Example 1.

[Example 3]
Similar to Example 1, press sheets having a thickness of 0.5 mm and a thickness of 1 mm were prepared except that the second layer was changed to Kurapet (manufactured by Kuraray Co., Ltd.), which is a commercially available polyethylene terephthalate resin. A modified olefin adhesive was applied to one of these two types of press sheets and heat-sealed to produce laminated sheets having a total thickness of 1 mm and 2 mm, respectively, and each physical property was evaluated. The results are shown in Table 2. The flexural modulus of the second layer was 2260 MPa. A laminated mouthpiece having excellent moldability was obtained, and a sheet having a low impact resilience, excellent dentition surface mounting feeling, and excellent appearance such as transparency and non-coloring properties was obtained. Moreover, when the mouthpiece was attached, the fit was superior to that of the commercially available product or Example 1.

[Comparative Example 1]
A single-layer press sheet of 4-methyl-1-pentene / propylene copolymer (A) was prepared so as to have the same thickness as in the Examples, and each physical property was evaluated. This layer corresponds to the first layer in the laminated sheet. The results are shown in Table 2. Although the rebound resilience was low, the mouthpiece itself was easily deformed and the wearing feeling was good, but it showed adhesiveness over time.

[Comparative Example 2]
A single-layer press sheet was prepared in the same manner as in Comparative Example 1 except that Tuffmer [registered trademark] A4085S (manufactured by Mitsui Chemicals, Inc.), which is a commercially available soft polyolefin, was used as a single-layer resin, and each physical property was evaluated. did. This layer corresponds to the first layer in the laminated sheet. The results are shown in Table 2. Since the hardness was low, it was soft and a little air bubbles were mixed during molding. Moreover, the wearing feeling of the mouthpiece was equivalent to a commercially available soft type mouthpiece.

[Comparative Example 3]
A single-layer press sheet was prepared in the same manner as in Comparative Example 1 except that Tuftec [registered trademark] H1041 (Asahi Kasei Chemicals Co., Ltd.), which is a commercially available hydrogenated styrene elastomer, was used to evaluate each physical property. This layer corresponds to the first layer in the laminated sheet. The results are shown in Table 2. The mouthpiece was soft due to its low hardness, and became an opaque mouthpiece due to the characteristics of the material itself. Moreover, the wearing feeling of the mouthpiece was equivalent to a commercially available soft type mouthpiece.

[Comparative Example 4]
A single-layer press sheet was prepared in the same manner as in Comparative Example 1, except that Evaflex [registered trademark] EV550 (made by Mitsui DuPont Polychemical Co., Ltd.), which is a commercially available ethylene-vinyl acetate copolymer, Each physical property was evaluated. This layer corresponds to the first layer in the laminated sheet. The results are shown in Table 2. Since the hardness is low, it was soft and air bubbles were mixed during molding. It was inferior in transparency and non-coloring property, and the wearing feeling of the mouthpiece was equivalent to a commercially available soft type mouthpiece.

[Comparative Example 5]
A single-layer press sheet was prepared in the same manner as in Comparative Example 1 except that Clarity [registered trademark] LA2330 (manufactured by Kuraray Co., Ltd.), which is a commercially available acrylic thermoplastic elastomer, was used to evaluate each physical property. This layer corresponds to the second layer in the laminated sheet. The results are shown in Table 2. Since the degree of vacuum was insufficient, it was difficult to mold, and it was difficult to produce a mouthpiece that fits the dental model, and air bubbles were mixed in and partly whitened. Moreover, it was inferior to transparency and non-coloring property. The mouthpiece wearing feeling was inferior to the commercially available soft type mouthpiece and was hard and painful.

[Comparative Example 6]
A single-layer press sheet was prepared in the same manner as in Comparative Example 1 except that Capture Sheet Hard [registered trademark] (manufactured by Matsukaze Co., Ltd.), which is a commercially available polyethylene terephthalate sheet for mouthpiece, was used, and each physical property was evaluated. This layer corresponds to the second layer in the laminated sheet. The results are shown in Table 2. Because it is hard, it is inferior to the mouthpiece, but it has excellent shape retention. Moreover, the water absorption was high and the transparency after water absorption was inferior.

[Comparative Example 7]
A single-layer press sheet was prepared in the same manner as in Comparative Example 1 except that Resamine P2588LS [registered trademark] (manufactured by Dainichi Seika Kogyo Co., Ltd.), which is a commercially available thermoplastic polyurethane, was evaluated. This layer corresponds to the first layer in the laminated sheet. The results are shown in Table 2. Although it was flexible and the mouthpiece wearing feeling was the same as that of a commercially available soft type mouthpiece, it had high water absorption and was inferior in transparency and non-coloring property.

[Comparative Example 8]
Each physical property was evaluated in the same manner as in Example 1 except that the resins used in Comparative Examples 6 and 7 were respectively molded into 0.5 mm and 1 mm thick sheets and laminated in the same manner as in the Examples. The results are shown in Table 2. Because of the lack of vacuum, floating occurred during molding, and it did not fit the jaw model. The water-absorbing property was high, the transparency and the non-coloring property were inferior, and the mouthpiece had a feeling of wearing due to a deformed portion during molding.

  As is apparent from Table 2, it is assumed that the mouthpiece composed of the laminated body for mouthpieces of the present invention shown in the examples can quickly fit the dentition because the stress relaxation rate of the first layer is low at room temperature. Since the hard material is used for the second layer at 37 ° C., the shape is maintained as compared with the case of only a single layer. In addition, since the rebound resilience is low, the biting comfort is excellent. Furthermore, since the low water absorption and the non-coloring property derived from foods, which are the characteristics of polyolefin, are excellent, they can be used for a long time without impairing the appearance.

Claims (6)

It consists of the 1st layer which consists of a composition (X) whose tensile elastic modulus or bending elastic modulus in 23 degreeC is less than 800 Mpa, and the thermoplastic resin (C) whose tensile elastic modulus or bending elastic modulus in 23 degreeC is 800 Mpa or more. It consists of at least two layers with the second layer,
The composition (X) comprises a structural unit (i) derived from 15 to 87 mol% 4-methyl-1-pentene and a structural unit (ii) derived from 13 to 85 mol% propylene (provided that 4-methyl-1-pentene / propylene copolymer (A) consisting of unit (i) and structural unit (ii) of 100 mol%), and thermoplastic resin And 50 to 0 parts by weight of at least one polymer (B) selected from the group consisting of rubber and rubber (provided that the total amount of the copolymer (A) and the polymer (B) is 100 parts by weight). Contains a laminated body for mouthpiece.   The laminate for a mouthpiece according to claim 1, wherein the thermoplastic resin (C) is at least one selected from the group consisting of polypropylene and polyethylene terephthalate.   The laminated body for a mouthpiece according to claim 1 or 2, wherein the thickness is 0.3 mm to 5.0 mm.   The mouthpiece which consists of a laminated body for mouthpieces of any one of Claims 1-3.   The mouthpiece according to claim 4, wherein an inner layer in contact with a dentition of the mouthpiece is the first layer, and an outer layer is the second layer. It is a manufacturing method of the mouthpiece of Claim 4 or 5 , Comprising: It heats until the said laminated body for mouthpieces is softened , A mouse | mouth is put along the dentition model or jaw model with the softened laminated body for mouthpieces. luma Usupisu manufacturing method to manufacture the pieces.