JP2007154013A - Copolymer for nonwoven fabric, copolymer composition for nonwoven fabric and nonwoven fabric - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolymer for nonwoven fabrics capable of producing a nonwoven fabric excellent in processability, stringiness, stretchability and flexibility. <P>SOLUTION: The copolymer for nonwoven fabrics is obtained by hydrogenating (A) at least two block copolymer blocks each mainly containing a unit derived from an aromatic vinyl compound and (B) at least one polymer block containing a unit derived from a conjugated diene compound and a unit derived from an aromatic vinyl compound, and the copolymer satisfies prescribed conditions. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a copolymer for nonwoven fabric, a copolymer composition for nonwoven fabric, a nonwoven fabric obtained by using these, and a patch.

  Conventionally, the demand for developing a nonwoven fabric having elasticity has been active in various industries. For this reason, many nonwoven fabrics made of various materials have been proposed. So far, stretchable nonwoven fabrics using crimped fibers have been developed, and it has been proposed to use this stretchable nonwoven fabric as a poultice base fabric. However, the physical properties such as stretchability of this stretchable nonwoven fabric still have room for improvement.

  Further, there are nonwoven fabrics obtained using polyamide, polyolefin, or polyester elastomers. However, the nonwoven fabrics obtained using these elastomers cannot be said to have sufficient stretchability. In addition, the nonwoven fabric obtained using polyurethane is favorable in terms of stretchability. However, since there is a problem that the thermal stability during processing is poor and decomposition gas is easily generated, it is necessary to improve the workability.

  As a related technique for solving the above problems, a stretchable nonwoven fabric containing a hydrogenated diene polymer and a crystalline low molecular weight polyolefin has been proposed (see, for example, Patent Document 1). Moreover, the nonwoven fabric obtained using the composition which contains an olefin type copolymer and a thermoplastic elastomer resin in a predetermined ratio is disclosed (for example, refer patent document 2).

However, even the nonwoven fabrics disclosed in Patent Documents 1 and 2 cannot be said to have sufficient stretchability and stringiness during processing. Further, for example, an elastic member such as a patch used by being stuck on the body cannot be said to have sufficient flexibility, and there is a problem that it cannot sufficiently follow the movement of the body.
Japanese Patent Laid-Open No. 11-12908 JP 2003-250879 A

  The present invention has been made in view of such problems of the prior art, and the object is to produce a nonwoven fabric excellent in processability, stringiness, stretchability, and flexibility. It is an object of the present invention to provide a non-woven fabric copolymer, a non-woven fabric copolymer composition, a non-woven fabric excellent in processability, stringiness, stretchability, and flexibility, and a patch.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have achieved the above-mentioned problems by using a hydrogenated diene copolymer obtained by hydrogenating a block copolymer having a specific block structure. As a result, the present invention has been completed.

  That is, according to this invention, the copolymer for nonwoven fabrics shown below, the copolymer composition for nonwoven fabrics, a nonwoven fabric, and a patch are provided.

[1] At least two polymer blocks (A) mainly composed of a structural unit derived from an aromatic vinyl compound, at least one structural unit derived from a conjugated diene compound, and a structural unit derived from an aromatic vinyl compound A copolymer for non-woven fabric satisfying the following conditions (1) to (6) obtained by hydrogenating a block copolymer containing: a polymer block (B) containing:
(1): The mass ratio of the polymer block (A) to the polymer block (B) is (A) / (B) = 5 to 45/95 to 55.
(2): The vinyl bond content of the polymer block (B) is 60% or more.
(3): The ratio of the structural unit derived from the aromatic vinyl compound contained in the polymer block (B) is 5 to 45% by mass.
(4): The weight average molecular weight is 5 to 500,000.
(5): Hydrogenation rate is 80% or more.
(6): The melt flow rate measured by 230 degreeC and a 21.2N load is 5-100 g / 10min.

  [2] (A) The nonwoven fabric copolymer according to [1] and (B) polyolefin resin in terms of mass ratio, (A) / (B) = 55 to 99 / 45-1 ( However, the copolymer composition for nonwoven fabrics contained in the ratio of (I) + (B) = 100).

  [3] A nonwoven fabric (hereinafter, also referred to as “first nonwoven fabric”) comprising the copolymer for nonwoven fabric according to [1].

  [4] A nonwoven fabric (hereinafter, also referred to as “second nonwoven fabric”) comprising the copolymer composition for nonwoven fabric according to [2].

  [5] A patch comprising the nonwoven fabric according to [3] or [4], and an adhesive layer disposed on at least one surface of the nonwoven fabric.

  The nonwoven fabric copolymer of the present invention has an effect that it is possible to produce a nonwoven fabric excellent in processability, stringiness, stretchability, and flexibility. Moreover, the copolymer composition for nonwoven fabrics of the present invention has an effect that it is possible to produce a nonwoven fabric excellent in processability, stringiness, stretchability, and flexibility.

  The first and second nonwoven fabrics of the present invention have the effect of being excellent in processability, stringiness, stretchability, and flexibility. Moreover, the patch of the present invention has an effect that it is excellent in workability, stringiness, stretchability, and flexibility.

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention. The term “nonwoven fabric of the present invention (this embodiment)” means both the first nonwoven fabric and the second nonwoven fabric.

1. Copolymer for Nonwoven Fabric One embodiment of the copolymer for nonwoven fabric of the present invention comprises at least two polymer blocks (A) mainly composed of a structural unit derived from an aromatic vinyl compound, and at least one conjugated diene. A polymer block (B) containing a structural unit derived from a compound and a structural unit derived from an aromatic vinyl compound, and the following conditions (1) to (6) obtained by hydrogenating a block copolymer containing To meet. The details will be described below.
(1): The mass ratio of the polymer block (A) to the polymer block (B) is (A) / (B) = 5 to 45/95 to 55.
(2): The vinyl bond content of the polymer block (B) is 60% or more.
(3): The ratio of the structural unit derived from the aromatic vinyl compound contained in the polymer block (B) is 5 to 45% by mass.
(4): The weight average molecular weight is 5 to 500,000.
(5): Hydrogenation rate is 80% or more.
(6): The melt flow rate measured by 230 degreeC and a 21.2N load is 5-100 g / 10min.

(Polymer block (A))
(A) A block is a polymer block mainly composed of a structural unit derived from an aromatic vinyl compound. If this (A) block is a polymer block consisting essentially of a structural unit derived from an aromatic vinyl compound, a structural unit derived from a conjugated diene compound may be included in a part thereof. (A) The structural unit derived from the aromatic vinyl compound in the block is usually 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and 100% by mass. It is particularly preferred.

  Specific examples of the aromatic vinyl compound include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, vinylnaphthalene, vinylanthracene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like can be mentioned. Of these, styrene is preferable.

(Polymer block (B))
(B) A block is a polymer block containing a structural unit derived from a conjugated diene compound and a structural unit derived from an aromatic vinyl compound. The content of the structural unit derived from the aromatic vinyl compound in the block (B) is preferably 5 to 45%, more preferably 10 to 40%, and more preferably 10 to 30%. Particularly preferred. If it is less than 5%, the stringiness tends to deteriorate. On the other hand, if it exceeds 45%, the flexibility tends to deteriorate.

  Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-octadiene, and 1,3-hexadiene. 1,3-cyclohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myrcene, chloroprene and the like. Of these, 1,3-butadiene and isoprene are preferable.

  (B) The vinyl bond (1,2-vinyl bond and 3,4-vinyl bond) content of the block is 60% or more, preferably 65% or more, and more preferably 78% or more. (B) The softness | flexibility of the nonwoven fabric obtained using this copolymer for nonwoven fabrics will become inadequate that the vinyl bond content of a block is less than 60%. In addition, although it does not specifically limit about the upper limit of the vinyl bond content of (B) block, It is preferable that it is 99% or less.

(Block copolymer)
The copolymer for nonwoven fabric of this embodiment is obtained by hydrogenating the block copolymer which is a copolymer before hydrogenation. Specific examples of the block structure of this block copolymer include the following structural formulas (1) to (3).
(AB) _m ... Structural formula (1)
(AB) _m -Y Structural formula (2)
A- (BA) _n ... Structural formula (3)

  In the structural formulas (1) to (3), “A” is a polymer block (A) (hereinafter also referred to as “(A) block”), and “B” is a polymer block (B) ( Hereinafter, it is also referred to as “(B) block”), and “Y” is a residue of the coupling agent. “M” is an integer of 2 to 5, and “n” is an integer of 1 to 5.

  Here, two or more “(A) blocks” in the block copolymers represented by the structural formulas (1) to (3) may be the same and have different compositions or molecular weights. It may be. Similarly, when two or more “(B) blocks” are contained in the block copolymer, the two or more “(B) blocks” may be the same and have different compositions or molecular weights. There may be. Furthermore, other polymer blocks (hereinafter, also referred to as “(C) block”) other than the (A) block and the (B) block, such as a polymer in which a conjugated diene compound is hydrogenated, are blocks. One or two or more may be copolymerized in the copolymer terminal or in the block copolymer chain.

  The mass ratio of the block (A) and the block (B) constituting the block copolymer is (A) / (B) = 5-45 / 95-55, preferably (A) / (B) = 10-35. / 90-65, more preferably (A) / (B) = 15-30 / 85-70. When (A) / (B) = less than 5/95, there is no constraining phase and molding is difficult. On the other hand, if (A) / (B) = over 45/55, the flexibility deteriorates.

((I) Non-woven copolymer (hydrogenated diene copolymer))
The weight average molecular weight (Mw) of the nonwoven fabric copolymer of this embodiment is 5 to 500,000, preferably 70 to 300,000, and more preferably 90 to 200,000. When Mw is less than 50,000, when the copolymer for nonwoven fabric is pelletized, it becomes easy to block, and roll drawability deteriorates due to the adhesiveness between the obtained nonwoven fabrics. On the other hand, when the Mw exceeds 700,000, the moldability is lowered.

  Moreover, the hydrogenation rate of the copolymer for nonwoven fabrics of this embodiment is 80% or more, Preferably it is 90% or more, More preferably, it is 95% or more. If the hydrogenation rate is less than 80%, the stretchability, flexibility, heat resistance, and weather resistance of the nonwoven fabric obtained by using this copolymer for nonwoven fabric will be insufficient.

  The melt flow rate (MFR) measured by 230 degreeC and a 21.2N load of the copolymer for nonwoven fabrics of this embodiment is 5-100 g / 10min, Preferably it is 7-70 g / 10min, More preferably, it is 10 ~ 50 g / 10 min. If the MFR is less than 5 g / 10 min, the fluidity is poor and molding is difficult. On the other hand, if the MFR is more than 100 g / 10 min, there may be a problem in extrusion moldability such as drawdown.

  Moreover, the ratio (henceforth "total aromatic vinyl compound unit content") of all the structural units derived from the aromatic vinyl compound contained in the copolymer for nonwoven fabrics of this embodiment is 5-70. It is preferable that it is mass%, and it is still more preferable that it is 13-65 mass%. If the total aromatic vinyl compound unit content is less than 5% by mass, the stringiness tends to deteriorate. On the other hand, if the total aromatic vinyl compound unit content exceeds 70% by mass, the flexibility tends to deteriorate.

(Other ingredients)
The copolymer for nonwoven fabric of this embodiment can also mix | blend tackifier resin as needed. Examples of the tackifying resin include rosin resins, polyterpene resins, synthetic petroleum resins, coumarone resins, phenol resins, xylene resins, styrene resins, and isoprene resins. Of these, rosin resins, polyterpene resins, and synthetic petroleum resins are preferable, and resins having an aliphatic structure and / or an alicyclic structure are more preferable.

  Examples of the resin having an aliphatic structure and / or an alicyclic structure include a partially hydrogenated rosin, a fully hydrogenated rosin, and derivatives thereof for a rosin resin; a polyterpene resin, a cyclic terpene homopolymer, a cyclic resin Copolymers of terpenes and hydrogenated products thereof; in synthetic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, aliphatic-alicyclic copolymer resins, naphtha cracked oils and various terpenes And hydrogenated products of the copolymer. These tackifier resins may be used alone or in combination of two or more.

  If necessary, a liquid additive such as paraffinic oil or liquid low molecular weight polyolefin may be added to the copolymer for nonwoven fabric of this embodiment to improve workability. Moreover, various additives can be added as long as the amount is within the range that does not impair extensibility and flexibility. Additives include antioxidants, weathering agents, metal deactivators, UV absorbers, light stabilizers, bleed and bloom inhibitors, sealability improvers, crystal nucleating agents, flame retardants, antibacterial and antibacterial agents Mold, dispersant, softener, anti-coloring agent, organic fiber, composite fiber, inorganic whisker, glass beads, glass balloon, glass flake, asbestos, mica, calcium carbonate, talc, silica, calcium silicate, hydrotalcite, Mention may be made of fillers such as kaolin, diatomaceous earth, graphite, pumice, evo powder, cotton floc, cork powder, barium sulfate, polymer beads, or mixtures thereof, or other rubbery polymers. Specific examples of other rubbery polymers include SBR, NBR, BR, NR, IR, 1,2-polybutadiene, AR, CR, IIR and the like.

  Furthermore, a thermoplastic resin can also be added as needed. Specific examples of this thermoplastic resin include diene resin, polyvinyl chloride resin, polycarbonate resin, polyacetal resin, polyamide resin, polyester resin, polyether resin, polysulfone, polyphenylene sulfide, POM, and the like. Can do.

(Method for producing block copolymer)
The block copolymer which is a copolymer before hydrogenation of the copolymer for nonwoven fabrics of this embodiment is, for example, an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, octane; cyclopentane, methylcyclopentane, cyclohexane, In an inert organic solvent such as an alicyclic hydrocarbon solvent such as methylcyclohexane; or an aromatic hydrocarbon solvent such as benzene, xylene, toluene, ethylbenzene; and the like, an aromatic vinyl compound and a conjugated diene compound, or an aromatic vinyl compound The conjugated diene compound and other monomers copolymerizable therewith can be produced by living anion polymerization using an organic alkali metal compound as a polymerization initiator.

  Specific examples of the organic alkali metal compound used as the polymerization initiator include organic lithium compounds and organic sodium compounds. Of these, organic lithium compounds such as n-butyllithium, sec-butyllithium, and tert-butyllithium are preferable. There is no particular limitation on the amount of the organic alkali metal compound used, and various amounts can be used as necessary, but usually 0.02 to 15 parts by mass, preferably 0. 03 to 5 parts by mass are used.

  The polymerization temperature is generally −10 to 150 ° C., preferably 0 to 120 ° C. Furthermore, it is desirable that the polymerization atmosphere is replaced with an inert gas such as nitrogen gas. The polymerization pressure may be a pressure sufficient to maintain the monomer and the inert organic solvent in the liquid phase, and is not particularly limited. Further, the method for introducing the monomer into the polymerization system is not particularly limited. For example, the monomers can be charged into the polymerization system by a method such as batch, continuous, intermittent, or a combination thereof.

  Also, a copolymer obtained by allowing a coupling agent to act on the block copolymer obtained by the above method and binding the molecular chain of the block copolymer via a residue of the coupling agent Can also be used as a copolymer before hydrogenation. Specific examples of coupling agents include divinylbenzene, 1,2,4-trivinylbenzene, epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized linseed oil, benzene-1,2,4-triisocyanate. Narate, diethyl oxalate, diethyl malonate, diethyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, diethyl terephthalate, pyromellitic dianhydride, diethyl carbonate, 1,1,2,2-tetrachloroethane, 1,4-bis (trichloromethyl) benzene, trichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, (dichloromethyl) trichlorosilane, hexachlorodisilane, tetraethoxysilane, tetrachlorotin, 1,3-dichloro-2 -Propa Mention may be made of the emissions and the like. Of these, divinylbenzene, epoxidized 1,2-polybutadiene, trichlorosilane, methyltrichlorosilane, and tetrachlorosilane are preferable.

(Method for producing copolymer for non-woven fabric (hydrogenated diene copolymer))
The copolymer for nonwoven fabric of this embodiment can be manufactured by hydrogenating the block copolymer obtained by said method partially or selectively. There are no particular limitations on the conditions for the hydrogenation reaction. The hydrogenation reaction is usually performed in the presence of a hydrogenation catalyst under 20 to 150 ° C. and 0.1 to 10 MPa of hydrogen under pressure. The hydrogenation rate can be arbitrarily adjusted by changing the amount of hydrogenation catalyst used, the hydrogen pressure during the hydrogenation reaction, the reaction time, and the like.

  Examples of the hydrogenation catalyst include compounds containing any one of Group Ib, IVb, Vb, VIb, VIIb, and Group VIII metals, such as Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, and Re. , Compounds containing Pt atoms can be used. More specifically, for example, metallocene compounds such as Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, and Re; metals such as Pd, Ni, Pt, Rh, and Ru are made of carbon, silica, A supported heterogeneous catalyst supported on a support such as alumina or diatomaceous earth; a homogeneous Ziegler catalyst in which an organic salt of a metal element such as Ni or Co or an acetylacetone salt and a reducing agent such as organoaluminum is combined; Ru, Examples include organometallic compounds or complexes such as Rh; fullerenes or carbon nanotubes in which hydrogen is occluded. Among these, a metallocene compound containing any of Ti, Zr, Hf, Co, and Ni is preferable in that a hydrogenation reaction can be performed in a homogeneous system in an inert organic solvent. Furthermore, a metallocene compound containing any of Ti, Zr, and Hf is preferable. In particular, a hydrogenation catalyst obtained by reacting a titanocene compound and an alkyl lithium is preferable because it is an inexpensive and industrially particularly useful catalyst. In addition, although only 1 type may be used for a hydrogenation catalyst, 2 or more types can also be used together.

  After the hydrogenation reaction, the catalyst residue is removed as necessary, or a phenolic or amine-based antioxidant is added, and then a hydrogenated diene copolymer (copolymer for nonwoven fabric) is added from the reaction solution. Is isolated. Isolation of the hydrogenated diene copolymer can be carried out, for example, by adding acetone or alcohol to the reaction solution for precipitation, or by pouring the reaction solution into hot water with stirring and distilling off the solvent. it can.

  The copolymer for nonwoven fabric of the present embodiment is a copolymer in which a functional group such as an amino group, an alkoxysilyl group, a hydroxyl group, an acid anhydride group, or an epoxy group is introduced, that is, a modified hydrogenated diene copolymer. It may be. Specific examples of the modified hydrogenated diene copolymer include the following copolymers ((a) to (f)).

  (A) A copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound in the presence of an organic alkali metal compound having an amino group, and hydrogenating the obtained copolymer.

  (B) A copolymer obtained by copolymerizing a vinyl aromatic compound, a conjugated diene compound, and an unsaturated monomer having an amino group in the presence of an organic alkali metal compound, and hydrogenating the obtained copolymer. Coalescence.

  (C) A vinyl aromatic compound and a conjugated diene compound are copolymerized in the presence of an organic alkali metal compound, and a copolymer obtained by reacting an alkoxysilane compound with an active point of the obtained copolymer is obtained. A copolymer obtained by hydrogenating a copolymer.

  (D) A copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound in the presence of an organic alkali metal compound and reacting an epoxy compound or a ketone compound with the active point of the obtained copolymer. A copolymer obtained by hydrogenating the copolymer.

  (E) A copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound in the presence of an organic alkali metal compound and hydrogenating the resulting polymer, a (meth) acryloyl group-containing compound, an epoxy group A copolymer obtained by reacting at least one selected from a containing compound and maleic anhydride in a solution or a kneader such as an extruder.

(F) A vinyl aromatic compound and a conjugated diene compound are copolymerized in the presence of an organic alkali metal compound, and epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized linseed oil, benzene as a coupling agent By using -1,2,4-triisocyanate, diethyl oxalate, diethyl malonate, diethyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, diethyl terephthalate, pyromellitic dianhydride, etc. A copolymer having a functional group such as —OH group, —NH—CO— group, —NH— group, —NH ₂ group or the like introduced in the center of the molecular chain.

  When the copolymer for nonwoven fabric of the present embodiment is the above-described modified hydrogenated diene copolymer, the ratio of the functional group in the modified hydrogenated diene copolymer is the ratio of the modified hydrogenated diene copolymer. It is preferable that it is 0.001-10 mol% with respect to the molecule | numerator which comprises a polymer, It is more preferable that it is 0.005-8 mol%, It is especially preferable that it is 0.01-5 mol%. .

2. Next, the copolymer composition for nonwoven fabric of the present invention will be described. In one embodiment of the copolymer composition for nonwoven fabric of the present invention, (a) the above-mentioned copolymer for nonwoven fabric and (b) a polyolefin-based resin are (a) / (b) = 55 by mass ratio. It is contained in a ratio of ˜99 / 45 to 1 (however, (A) + (B) = 100). The details will be described below.

((B) Polyolefin resin)
(B) A polyolefin-based resin is a resin obtained by polymerizing one or more monoolefins by either a high pressure method or a low pressure method. (B) Preferable examples of the polyolefin resin include polyethylene, polypropylene, and polybutene-1. (B) The polyolefin resin may be a homopolymer or a copolymer obtained by copolymerizing another monomer. Specific examples of other monomers constituting this copolymer include ethylene (except when the main polymer is polyethylene), propylene (except when the main polymer is polypropylene), 1-butene (main weight). Linear olefins such as 1-pentene, 1-hexene, 1-heptene, 1-octene; 4-methyl-1-pentene, 2-methyl-1- Branched α-olefins such as propene, 3-methyl-1-pentene, 5-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene; acrylic acid, methacrylic acid, ethacryl Monocarboxylic acids such as acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid and monoesters thereof; methyl methacrylate, Esters of acrylic acid and methacrylic acid such as ethyl acrylate; vinyl esters of saturated carboxylic acids such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene, α-methylstyrene and p-methylstyrene; maleic anhydride, anhydrous Acid anhydrides such as itaconic acid, citraconic anhydride and aconitic anhydride; α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile; diene monomers such as 1,4-hexadiene, dicyclopentadiene and ethylidene norbornene; Examples include acrylamide, methacrylamide, and maleimide.

  These other monomers may be used alone or in combination of two or more. The proportion of structural units derived from these other monomers in the copolymer is preferably 20% by mass or less, and more preferably 10% by mass or less. The copolymerization mode of the copolymer may be any of random type, block type, graft type, or mixed type thereof.

  (B) Preferred examples of the copolymer used as the polyolefin-based resin include propylene-ethylene copolymer, 1-butene-propylene copolymer, 1-butene-ethylene copolymer, propylene-ethylene-1-butene. Copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate A copolymer etc. can be mentioned.

  (B) Polyolefin resins may be used singly or in combination of two or more. In addition, it is preferable that MFR measured by 230 degreeC and a 21.2N load of (b) polyolefin resin is 0.01-200 g / 10min, and it is 0.1-100 g / 10min. Further preferred.

(Copolymer composition for nonwoven fabric)
The copolymer composition for nonwoven fabrics of this embodiment is (i) / (b) = 55-99 / 45 by mass ratio of (a) copolymer for nonwoven fabrics and (b) polyolefin resin. 1, preferably (b) / (b) = 60 to 99/40 to 1, more preferably (b) / (b) = 70 to 99/30 to 1. Note that (A) + (B) = 100. The copolymer composition for nonwoven fabrics of this embodiment in which (a) a copolymer for nonwoven fabrics and (b) a polyolefin-based resin are blended at the above-mentioned mass ratio is compared with a single copolymer for nonwoven fabrics (a). Thus, the fluidity is improved and the processability is excellent. In addition, if it is less than (A) / (B) = 55/45, it causes deterioration of flexibility.

(Other ingredients)
If necessary, a liquid additive such as a tackifier resin, paraffinic oil or liquid low molecular weight polyolefin, and other various additives and thermoplastic resins are added to the copolymer composition for nonwoven fabric of this embodiment. be able to. In addition, as a component which can be added, the thing similar to what was described by the copolymer for nonwoven fabrics of this embodiment can be mention | raise | lifted.

(Method for producing copolymer composition for nonwoven fabric)
The copolymer composition for nonwoven fabric of this embodiment can be manufactured by melt-kneading (b) the copolymer for nonwoven fabric and (b) polyolefin resin, for example. In kneading, a single screw extruder, a twin screw extruder, a kneader, a roll, or the like can be used. The above-mentioned various additives and various polymers include, for example, these additives and the like previously blended in (a) a copolymer for nonwoven fabric and (b) a polyolefin resin, or (a) a copolymer for nonwoven fabric. What is necessary is just to mix | blend at the time of kneading | mixing with coalescence and (b) polyolefin resin.

3. Next, the first nonwoven fabric and the second nonwoven fabric of the present invention will be described. One embodiment of the first nonwoven fabric of the present invention comprises the above-mentioned copolymer for nonwoven fabric. Moreover, the 2nd nonwoven fabric of this invention consists of the above-mentioned copolymer composition for nonwoven fabrics. For this reason, the first nonwoven fabric and the second nonwoven fabric of the present invention are excellent in processability, stringiness, stretchability, and flexibility. Therefore, the nonwoven fabric of the present invention is suitable as a patch material such as a compress base fabric. Moreover, since it is excellent in thermal stability as compared with urethane elastic fiber or the like, there is no problem of gas generation or decomposition during processing. Furthermore, since weather resistance is also favorable, it can be used for every use. Specifically, in addition to the adhesive material, various masks for surgical and industrial use; various filters such as air filters for clean rooms, blood filters, oil / water separation filters; battery electrode separators; clothing insulating materials and heat insulating materials Various clothing materials such as protective clothing and disposable underwear; wipers, oil-absorbing materials / oil-water separators, sheets, diapers, synthetic leather, surgical gowns, medical supplies and other sanitary materials such as medical disposable products; Various heat insulating materials such as heat insulating materials; Food packaging materials such as coffee bags and cooked rice packaging sheets; Electret processed electret filters; Automotive ceiling skin materials, sound insulating materials, base materials, heat insulating materials, cushion materials, speaker dustproof materials Various automotive parts such as air cleaner materials, insulator skins, backing materials, adhesive non-woven sheets, door trims, etc. Various cleaning materials such as copying machine cleaning materials; carpet surface materials / backing materials, agricultural distribution, wood drain materials, sports shoe skins and other shoe materials, bag materials, industrial sealing materials, wiping materials, etc. It can be used suitably for a use.

(Nonwoven fabric manufacturing method)
The nonwoven fabric of this embodiment can be manufactured by various shaping | molding methods. Specifically, a direct molding method called “melt blown” is suitable. This melt blown refers to a method of producing a nonwoven fabric by melt spinning a thermoplastic material, collecting the fiber stream with a high-speed gas into a sheet shape. In the case of this melt blown, it is possible to produce each composition, liquid additive and the like by kneading in advance with an extruder or the like, and supply the obtained composition to an extruder for producing a nonwoven fabric. . Moreover, each component etc. which were measured and mixed can also be directly supplied to the nonwoven fabric manufacturing extruder for production.

  In order to produce a composition by kneading each component or liquid additive in advance with an extruder or the like, a conventionally known kneader such as an extruder, a kneader or a Banbury mixer, or a kneader in combination of these is used. be able to. In the production of this composition, the respective components may be mixed at once, or the optional components may be premixed and then the remaining components may be added and mixed. The most preferred mixing device is a single or twin screw extruder. By using a single-screw or twin-screw extruder, continuous and efficient kneading can be performed.

  The nonwoven fabric of this embodiment can be molded with the same ease as polypropylene or the like, which is a normal nonwoven material. Accordingly, it is possible to obtain a nonwoven fabric having an arbitrary property by appropriately changing the melt viscosity, the polymer discharge amount, the amount of jetting fluid, and the like. Moreover, electret processing is also possible, and when electret processing is performed, an electret nonwoven fabric can be obtained.

4). Next, the patch of the present invention will be described. One embodiment of the patch of the present invention comprises the above-described nonwoven fabric and an adhesive layer disposed on at least one surface of the nonwoven fabric. For this reason, the patch of this embodiment is excellent in workability, stringiness, stretchability, and flexibility.

(Adhesive layer)
The pressure-sensitive adhesive layer is preferably a coating layer having excellent permeability. Specific examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, gel-like pressure-sensitive adhesives, and the like, which are appropriately selected depending on the purpose of use. For example, when the patch is used as a transdermally absorbable preparation, the adhesive may be selected so that the drug is most effectively absorbed from the skin and the irritation to the skin is reduced. Further, the adhesive layer may contain a transdermally absorbable drug depending on the application.

(Manufacturing method of patch material)
As a method of providing the pressure-sensitive adhesive layer on the surface of the nonwoven fabric, a method of directly applying the pressure-sensitive adhesive to the nonwoven fabric, or forming a pressure-sensitive adhesive layer on the release paper and laminating the release paper on the nonwoven fabric, this pressure-sensitive adhesive layer Can be used. In addition, an adhesive layer can also be arrange | positioned by patterns, such as a linear form, a mesh form, and a dot form, on the whole surface of a nonwoven fabric, or a part. The thickness of the pressure-sensitive adhesive layer is preferably 0.01 to 2 mm, more preferably 0.015 to 1 mm.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

[Hydrogenation rate]: Carbon tetrachloride solution was used, and calculated from 270 MHz, ¹ H-NMR spectrum.

  [Melt flow rate (MFR)]: Measured according to JIS K7210 at 230 ° C. and 21.2 N load.

[Total bound styrene content]: Using a carbon tetrachloride solution, the content was calculated from a 270 MHz, ¹ H-NMR spectrum.

[(B) Styrene content in block]: Calculated from the charged amount using the following formula.
(B) Styrene content in block (%) = (total amount of styrene contained in block (B)) / ((B) total amount of block charged) × 100

[(A) / (B) ratio]: Calculated from the charged amount using the following formula.
(A) / (B) ratio = ((A) total amount of charged blocks) / ((B) total charged amount of blocks)

  [Vinyl bond content]: The vinyl bond (1,2-bond and 3,4-bond) content was calculated by the Hampton method using infrared analysis.

  [Weight average molecular weight (Mw)]: It was determined in terms of polystyrene using gel permeation chromatography (room temperature GPC, column: GMH-XL (trade name), manufactured by Tosoh Corporation).

[Processability]: Processability and stringiness in a meltblown were evaluated according to the following criteria.
A: Good workability and stringiness were obtained, and a good nonwoven fabric could be obtained under a wide range of conditions.
○: The nonwoven fabric could be obtained under normal conditions without problems in workability and stringiness.
(Triangle | delta): There was almost no problem in workability and stringing property, and the nonwoven fabric was able to be obtained although it was difficult, for example, a fiber aggregated and stuck a little.
X: A uniform nonwoven fabric could not be obtained under normal conditions such as low fluidity at the time of melting or agglomeration / glue of ejected fibers.

[Elongation, stress at 10% elongation]: Three test pieces each having a width of 2.5 cm and a length of 20 cm were prepared in the longitudinal direction and the transverse direction of the nonwoven fabric. A tensile tester (trade name “Autograph AG-G”, manufactured by Shimadzu Corporation) was used, the gap between the chucks was set to 10 cm, and one of the test pieces was fixed. The film was stretched at a tensile speed of 300 mm / min, and the maximum elongation was measured. Further, the stress at the time of 10% elongation was measured and converted to the stress of the nonwoven fabric per unit weight (g / cm ² ), and the stress at the time of 10% elongation (g / cm) / (g / cm ² ) did. This operation was performed three times with the test piece in each direction, and the geometric mean value of each was obtained.

Example 1
An autoclave with an internal volume of 50 liters was charged with 25 kg of degassed / dehydrated cyclohexane and 450 g of styrene, 300 g of tetrahydrofuran and 3.5 g of n-butyllithium were added, and adiabatic polymerization from 50 ° C. was carried out for 20 minutes. After the temperature of the reaction solution was 20 ° C., 3250 g of 1,3-butadiene and 1000 g of styrene were added to perform adiabatic polymerization. After the conversion rate was almost 100%, 300 g of styrene was further added for polymerization. After the completion of the polymerization, hydrogen gas was supplied at a pressure of 0.4 MPa-G and stirred for 20 minutes to react with the polymer terminal lithium alive as a ribin anion to obtain lithium hydride. After setting the reaction solution to 90 ° C., a hydrogenated diene copolymer (H-1) was obtained by performing a hydrogenation reaction using a titanocene compound described in JP-A 2000-37632.

  The obtained hydrogenated diene copolymer (H-1) has a total bond styrene content of 35%, a vinyl bond content of 74%, a hydrogenation rate of 98%, an MFR of 30 g / 10 min, and a weight average molecular weight of 130,000. The styrene content in the block (B) was 23%, and the (A) / (B) ratio of the copolymer before hydrogenation was 15/85.

(Example 2, Example 3, Comparative Examples 1-5)
A hydrogenated diene copolymer (H-2, shown in Table 1) was prepared in the same manner as in Production Example 1 except that the monomer amount, tetrahydrofuran addition amount, catalyst amount, polymerization temperature, polymerization time and the like were changed. H-3, R-1 to R-5) were produced. In addition, Table 1 shows the measurement results of the physical properties of these hydrogenated diene copolymers.

Example 4
Pellets were obtained by melt-kneading the hydrogenated diene copolymer (H-1) obtained in the above production example using a single screw extruder. After the pellets obtained using the extruder for producing a nonwoven fabric were melted, a nonwoven fabric (Example 4) having a basis weight of 200 g / m ² was obtained using a melt blown spinning device. The processability of the obtained nonwoven fabric (Example 4) is “◯”, the longitudinal elongation is 750%, the transverse elongation is 710%, and the longitudinal elongation is 10%. / Cm) / (g / cm ² ), and the stress at the time of 10% elongation in the transverse direction was 0.9 (g / cm) / (g / cm ² ).

(Examples 5-6, Comparative Examples 6-10)
Nonwoven fabrics having a basis weight of 200 g / m ² (Examples 5 to 6 and Comparative Examples 6 to 10) in the same manner as in Example 1 except that the hydrogenated diene copolymers shown in Table 2 were used. ) Table 2 shows the measurement results and evaluation results of various physical properties of the obtained nonwoven fabric.

(Example 7)
Pellets were prepared by melt-kneading 90 parts of the hydrogenated diene copolymer (H-1) obtained in the above production example and 10 parts of PP-1 as a polyolefin resin using a single screw extruder. Obtained. After the pellets obtained using the extruder for producing a nonwoven fabric were melted, a nonwoven fabric (Example 7) having a basis weight of 200 g / m ² was obtained using a melt blown spinning device. The processability of the obtained nonwoven fabric (Example 7) is “は”, the longitudinal elongation is 700%, the transverse elongation is 680%, and the longitudinal elongation is 10%. / Cm) / (g / cm ² ), and the stress at 10% elongation in the lateral direction was 1.4 (g / cm) / (g / cm ² ).

(Examples 8 to 10, Comparative Example 11)
A basis weight of 200 g / m ² was obtained in the same manner as in Example 7 except that the hydrogenated diene copolymer and polyolefin resin of the type shown in Table 3 were used in the amounts shown in Table 3, respectively. Nonwoven fabrics (Examples 8 to 10, Comparative Example 11) were obtained. Table 3 shows the measurement results and evaluation results of various physical properties of the obtained nonwoven fabric. In Table 3, “PP-1” and “PE-1” are shown below.

“PP-1”: propylene-ethylene random copolymer, trade name “MG03B”, manufactured by Nippon Polypro Co., Ltd., MFR: 30 g / 10 minutes (190 ° C., 21.2 N load)
“PE-1”: low density polyethylene, trade name “LJ902N”, manufactured by Nippon Polyethylene Co., Ltd., MFR: 45 g / 10 min (190 ° C., 21.2 N load)

  As shown in Table 2, it is clear that the nonwoven fabrics of Examples 4 to 6 have excellent processability and good stretchability as compared with the nonwoven fabrics of Comparative Examples 6 to 10. Moreover, it is clear that the nonwoven fabrics of Examples 4 to 6 have a small stress when stretched by 10% and have excellent flexibility.

  Moreover, as shown in Table 3, when a specific polyolefin resin is blended with a hydrogenated diene copolymer (copolymer for nonwoven fabric), processability is maintained while maintaining high stretchability and flexibility. It is clear that is further improved.

  Non-woven fabrics of the present invention are adhesive materials; various masks for surgical and industrial use; various filters such as clean room air filters, blood filters, oil-water separation filters; battery electrode separators; clothing insulating materials, heat insulating materials, protective clothing Various clothing materials such as disposable underwear; wipers, oil-absorbing materials / oil-water separators, sheets, diapers, synthetic leather, surgical gowns, medical disposables such as disposable medical products; Food packaging materials such as coffee bags and cooked rice packaging sheets; electret filters with electret processing; automotive ceiling skin materials, sound insulation materials, base materials, heat insulation materials, cushioning materials, speaker dustproof materials, air Various automotive parts such as cleaner materials, insulator skins, backing materials, adhesive nonwoven fabric sheets, door trims, etc. Suitable for various cleaning materials such as machine cleaning materials; carpet surface materials / backing materials, agricultural cloth, wood drain materials, sports shoe skins and other shoe materials, bag materials, industrial sealing materials, wiping materials, etc. is there.

Claims (5)

At least two polymer blocks (A) mainly composed of structural units derived from an aromatic vinyl compound;
A polymer block (B) comprising at least one structural unit derived from a conjugated diene compound and a structural unit derived from an aromatic vinyl compound;
A copolymer for nonwoven fabric that satisfies the following conditions (1) to (6) by hydrogenating a block copolymer containing:
(1): The mass ratio of the polymer block (A) to the polymer block (B) is (A) / (B) = 5 to 45/95 to 55.
(2): The vinyl bond content of the polymer block (B) is 60% or more.
(3): The ratio of the structural unit derived from the aromatic vinyl compound contained in the polymer block (B) is 5 to 45% by mass.
(4): The weight average molecular weight is 5 to 500,000.
(5): Hydrogenation rate is 80% or more.
(6): The melt flow rate measured by 230 degreeC and a 21.2N load is 5-100 g / 10min. (A) the nonwoven fabric copolymer according to claim 1;
(B) a polyolefin-based resin;
In a mass ratio (i) / (b) = 55 to 99/45 to 1 (provided that (b) + (b) = 100).   A nonwoven fabric comprising the copolymer for nonwoven fabric according to claim 1.   A nonwoven fabric comprising the copolymer composition for nonwoven fabric according to claim 2. The nonwoven fabric according to claim 3 or 4,
An adhesive layer disposed on at least one surface of the nonwoven fabric;
A patch with