JPH0976436A - Uniaxially oriented material, laminate, nonwoven fabric, woven fabric and reinforcing laminate using them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a uniaxially oriented material, its laminated, nonwoven fabric, woven fabric and reinforcing laminate using them which have an excellent tear resistance and adhesive strength and make it possible to be accelerated to be manufactured without trouble. SOLUTION: This uniaxially oriented material 1 is formed by laminating an adhesive layer (II) 3 having a lower melting point than that of the thermoplastic resin of a resin layer (I) 2 and containing specific composition on at least one side surface of the layer (I) 2. The laminate, nonwoven fabric or woven fabric is obtained by laminating a plurality of the materials 1 via the layers (II) 3 with each other. The reinforcing laminate is obtained by laminating the laminate, nonwoven fabric or woven fabric on a base material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminate, a nonwoven fabric and a woven fabric which are excellent in adhesive strength and low temperature heat sealability and have high mechanical strength such as tear strength, and a reinforced laminate using them, and particularly, The present invention relates to a laminate having excellent adhesive strength of longitudinal and transverse fibers, low-temperature heat-sealing property, moldability, etc., a nonwoven fabric and a woven fabric, and a reinforced laminate containing them and a substrate such as paper, other plastics and foils.

[0002]

2. Description of the Related Art Conventionally, a uniaxially stretched film of a thermoplastic resin or a reinforced film obtained by laminating low-density polyethylene on a reinforced film obtained by laminating the same, or a reinforced sheet of the above reinforced film and paper, a foamed sheet, an aluminum foil, etc. BACKGROUND OF THE INVENTION Reinforced laminates obtained by laminating a base material such as a metal foil have been utilized as a leisure underlayment sheet, a protective sheet (hood) for vehicles, an agricultural covering material, a synthetic resin pellet bag, a cement bag and the like. Further, as a non-woven fabric obtained by splitting a longitudinal or transverse uniaxially stretched film, or a non-woven fabric or woven fabric obtained by laminating or woven longitudinally uniaxially stretched tape, low density polyethylene by high pressure radical polymerization method is laminated on both sides of high density polyethylene. A polyethylene nonwoven fabric or woven fabric has been developed, which is obtained by stretching the film and then splitting the resulting mesh film and laminating them so that the orientation axes cross each other and heat-sealing them. Green cover, filter, drainer bag, various bags,
It is used for agricultural and horticultural materials such as oil adsorbents, flower wraps, house wraps, and construction materials. However, in recent years, it has been desired to increase the adhesive strength of a composite product obtained by laminating a stretched film and another substrate, and when using a composite product or a single product as a bag, it is necessary to increase the bag-making speed. It is strongly desired to improve the low temperature heat sealability and the adhesive strength of the seal portion. Further, in the case of non-woven fabrics and woven fabrics, it is desired to improve the above-mentioned various physical properties as well as improve the adhesive strength at the intersections of the longitudinal and transverse fibers of the non-woven fabrics and woven fabrics. Furthermore, with the recent widespread use of these non-woven fabrics and woven fabrics themselves as drainage bags for kitchens and agricultural materials, functionalization such as coloring and imparting weather resistance to laminates, non-woven fabrics and woven fabrics has become possible. Is requested. But,
When a pigment or a weatherproofing agent is added to a non-woven fabric or the like, there is a problem that eye splits are accumulated in the splitting tool at the time of splitting (splitting), and a splitting defective portion or white powder is generated.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been studied earnestly in order to solve the above-mentioned problems, and as a result, by improving the adhesive layer of a multilayer film formed by using an oriented resin having high crystallinity as an base, It was found that a material such as a film-forming step and a fiber-splitting step during the production of a non-woven fabric can be solved, and that a material having excellent tear resistance, adhesive strength, etc., and sufficiently satisfying the above requirements can be obtained. The invention has been completed. That is, the first object of the present invention is to provide a uniaxially oriented body excellent in tear resistance, adhesive strength, etc., a laminate thereof,
A non-woven fabric and a woven fabric are provided. Second of the present invention
The purpose of each is film forming, stretching, splitting, lamination thermocompression bonding, etc. when laminating a laminate, manufacturing a nonwoven fabric, or coloring a laminate, a nonwoven fabric or a woven fabric to impart weather resistance. It is an object of the present invention to provide a laminate, a non-woven fabric and a woven fabric which prevent troubles in the process, improve the adhesive strength of longitudinal and transverse fibers of the laminate, the non-woven fabric or the woven fabric, and have excellent low temperature heat sealability and the like. That is, problems such as bubble stability and other film-forming properties in the film-forming process, problems such as alignment unevenness and alignment breakage in the alignment process, and split defect or split fiber breakage in the split or slit process. Problems related to fineness, and when pigments and weatherproofing agents are added, defective splitting parts or white powder may occur due to accumulation of eye blemishes in the splitting tool during splitting (splitting), or product nonwoven fabrics, etc. It is to eliminate various problems such as a decrease in adhesive strength. A third object of the present invention is to provide a uniaxially oriented body,
It is intended to achieve speeding up, etc. when making a bag of a laminated body, a non-woven fabric or a woven fabric, or a composite product with another substrate. A fourth object of the present invention is to provide the above uniaxially oriented body, and a reinforced laminate having a high adhesive strength between a nonwoven fabric or a woven fabric using the same and a substrate.

[0004]

According to claim 1 of the present invention, an adhesive layer (II) having a melting point lower than that of the thermoplastic resin of the resin layer (I) is provided on at least one surface of the thermoplastic resin layer (I). A uniaxially oriented body formed by laminating, or a laminated body obtained by laminating a plurality of the uniaxially oriented bodies with an adhesive layer (II) interposed therebetween. [Adhesive layer (II)] (1) 100 to 20% by weight of ethylene / α-olefin copolymer (A) having the following properties (a) Density (d) 0.86 to 0.94 g / cm ³ (b) ) Melt flow rate (MFR) 0.01 to 100 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.8 to 3.5 (d) Composition distribution parameter (Cb) 1.10 to 2.00 (2) Composition containing 80% by weight or less of another olefin polymer (B)

According to claim 2 of the present invention, the ethylene / α-
Amount of olefin copolymer (A) soluble in o-dichlorobenzene (ODCB) at 25 ° C (X, wt%)
And d and MFR, the following formula [I] or [II]
The laminated body according to claim 1, which has a relationship represented by:

[Equation 2]

[0006] Claim 3 of the present invention is the ethylene · α-
Olefin copolymer (A) is a continuous temperature rising elution fractionation method (T
The laminated body according to claim 2, which has a plurality of peaks in an elution temperature-elution amount curve by REF).

A fourth aspect of the present invention is characterized in that the olefin polymer (B) is at least one selected from the following ethylene polymers. It is a laminated body of. [Ethylene Polymer] (1) Density 0.86 polymerized using Ziegler type catalyst
To 0.95 g / cm ³ of ethylene / α-olefin copolymer (B ₁ ) (2) Low-density polyethylene by high-pressure radical polymerization, ethylene / vinyl ester copolymer, or ethylene and α, β-unsaturated carboxylic acid Alternatively, a copolymer with its derivative (B ₂ )

A fifth aspect of the present invention is the laminate according to any one of the first to fourth aspects, in which the uniaxially oriented body has an orientation magnification of 1.1 to 15.

According to a sixth aspect of the present invention, the thickness of the thermoplastic resin layer (I) of the uniaxially oriented body is 20 to 100 μm,
The laminate according to any one of claims 1 to 5, wherein the adhesive layer (II) has a thickness of 3 to 60 µm.

According to a seventh aspect of the present invention, an adhesive layer (II) having a melting point lower than that of the thermoplastic resin of the resin layer (I) is laminated on at least one surface of the thermoplastic resin layer (I). At least one kind of uniaxially oriented body selected from a longitudinal uniaxially oriented reticulated film (a), a lateral uniaxially oriented reticulated film (b) and a uniaxially oriented multilayer tape (c), or an adhesive layer (II) for mutually bonding the uniaxially oriented body. It is a non-woven fabric or a woven fabric that is formed by laminating a plurality of sheets. [Adhesive layer (II)] (1) 100 to 20% by weight of ethylene / α-olefin copolymer (A) having the following properties (a) Density (d) 0.86 to 0.94 g / cm ³ (b) ) Melt flow rate (MFR) 0.01 to 100 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.8 to 3.5 (d) Composition distribution parameter (Cb) 1.10 to 2.00 (2) Composition containing 80% by weight or less of another olefin polymer (B)

According to claim 8 of the present invention, at least one kind of uniaxially oriented body selected from the longitudinal uniaxially oriented network film (a), the lateral uniaxially oriented network film (b) and the uniaxially oriented multilayer tape (c) is mutually present. The non-woven fabric or woven fabric according to claim 7, wherein the non-woven fabric or the woven fabric is laminated or woven so that the orientation axes intersect with each other via the adhesive layer (II).

A ninth aspect of the present invention is characterized in that the thermoplastic resin layer (I) of the uniaxially oriented body is blended with at least one additive selected from a filler, a pigment and a weathering agent. Item 1. A uniaxially oriented body according to any one of Items 1 to 8,
It is a laminate, a non-woven fabric or a woven fabric.

According to a tenth aspect of the present invention, a uniaxially formed by laminating an adhesive layer (II) having a melting point lower than that of the thermoplastic resin of the resin layer (I) on at least one surface of the thermoplastic resin layer (I). Reinforced laminate including an oriented body or a laminated body formed by laminating a plurality of the above uniaxially oriented bodies with an adhesive layer (II) interposed therebetween, at least one kind of oriented material selected from a nonwoven fabric and a woven fabric, and a substrate. It is the body. [Adhesive layer (II)] (1) 100 to 20% by weight of ethylene / α-olefin copolymer (A) having the following properties (a) Density (d) 0.86 to 0.94 g / cm ³ (b) ) Melt flow rate (MFR) 0.01 to 100 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.8 to 3.5 (d) Composition distribution parameter (Cb) 1.10 to 2.00 (2) Composition containing 80% by weight or less of another olefin polymer (B)

The present invention will be described in more detail below. The resin used in the thermoplastic resin layer (I) in the present invention is a crystalline thermoplastic resin having orientation, and is a high, medium or low density polyethylene, polypropylene, polybutene-1, poly-
Homopolymers of α-olefins such as 4-methylpentene-1, polyhexene-1; copolymers of ethylene with other α-olefins, copolymers of propylene with other α-olefins such as ethylene, etc. Polyolefins such as copolymers of α-olefins; and oriented resins having crystallinity such as polyamide, polyester and polyvinyl alcohol. Among these, particularly, propylene homopolymers, propylene-based polymers such as copolymers containing propylene as a main component with other α-olefins, and ethylene homopolymers having a density of 0.94 to 0.98 g / cm ^3. An ethylene polymer such as a polymer or a copolymer having ethylene as a main component with another α-olefin, or a mixture thereof is preferable. Examples of the α-olefin include ethylene, propylene, butene-1,4-methylpentene-1, and hexene-
Those having 2 to 10 carbon atoms such as 1 are preferable. In particular, ethylene-based polymers such as ethylene homopolymers having a density of 0.94 to 0.98 g / cm ³ and copolymers containing ethylene as a main component with other α-olefins are preferable. The content of these comonomers is selected from the range of 3 to 15 mol%. Also,
Propylene-based polymer and / or density 0.94 to 0.9
Melt flow rate of ethylene polymer of 8 g / cm ³ (M
FR) is 0.01 to 30 g / 10 minutes, preferably 0.1 to 2
It is selected from the range of 0 g / 10 minutes, more preferably 0.2 to 10 g / 10 minutes.

The ethylene / α-olefin copolymer (A) used in the adhesive layer (II) in the present invention is a copolymer of ethylene and at least one α-olefin having 3 to 20 carbon atoms. is there. The carbon number of the α-olefin is preferably 3 to 12, specifically, propylene, butene-1,
4-methyl-pentene-1, hexene-1, octene-
1, decene-1, dodecene-1 and the like. Further, the content of these α-olefins is usually 3 in total.
It is selected from the range of 0 mol% or less, preferably 3 to 20 mol%.

The density of [0016] used in the present invention the ethylene · alpha-olefin copolymer (A), 0.86~0.94g / cm ^3, preferably in the range of 0.89~0.93g / cm ^3. If the density is less than 0.86 g / cm ³ , the obtained laminate, non-woven fabric or woven fabric may have poor anti-blocking property, heat resistance may be impaired, and adhesive strength with the substrate may be low. Also, 0.
When it exceeds 94 g / cm ³ , the low temperature heat sealability is poor.

Ethylene / α-olefin copolymer (A)
Has an MFR of 0.01 to 100 g / 10 min, preferably 0.1.
It is in the range of 1 to 50 g / 10 min. MFR is 0.01g / 10m
If it is less than in, the melt viscosity is high and the moldability is poor.
If it exceeds g / 10min, the moldability and mechanical strength are poor.

Ethylene / α-olefin copolymer (A)
The molecular weight distribution Mw / Mn of is determined by gel permeation chromatography (GPC).
And the number average molecular weight (Mn) are calculated and calculated as the ratio of the two. In the present invention, the above Mw / Mn is 1.8 to 3.
5, and preferably in the range of 2.0 to 3.0, more preferably 2.2 to 2.8. If Mw / Mn is less than 1.8, the moldability is poor, and if it exceeds 3.5, the mechanical strength is poor.

The composition distribution parameter (Cb) of the ethylene / α-olefin copolymer (A) used in the present invention.
Is 1.10 to 2.00, preferably 1.12-1.
70, more preferably 1.15 to 1.50. When Cb is less than 1.10, the hot tack property is poor,
If it exceeds 2.00, there is a concern that a polymer gel will be formed in the molded product.

The method for measuring the above composition distribution parameter (Cb) is as follows. (1) Fractional elution A sample is added together with a heat stabilizer to ODCB so that the sample concentration becomes 0.2% by weight, and heated and dissolved at 135 ° C. This heated solution was transferred into a column filled with diatomaceous earth (Celite 545) to fill the column, and then 0.1 ° C / min
The sample is deposited and deposited on the surface of Celite by cooling to 25 ° C at a cooling rate of. Next, ODCB is flown through this column at a constant flow rate, and the column temperature is raised stepwise at 5 ° C. intervals up to 120 ° C., and a solution in which the sample is dissolved is collected at each temperature. After cooling these solutions, the sample is reprecipitated with methanol, filtered and dried to obtain the sample at each elution temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) are determined for the separated samples. The degree of branching is measured by ¹³ C-NMR.

(2) Correction of degree of branching For each fraction collected in the temperature range from 30 ° C. to 90 ° C. by the above method, the degree of branching was plotted against the elution temperature, and the correlation was linearly calculated by the method of least squares. Approximate and create a calibration curve. The correlation coefficient of this approximation is sufficiently large. The value obtained from the elution temperature using this calibration curve,
The degree of branching of each fraction is used in the following calculation. The above correction is not performed for the fractions collected at an elution temperature of 95 ° C. or higher, because a linear relationship between the elution temperature and the degree of branching is not always established.

[0022] (3) Cb calculate the next relative to the weight fraction of each fraction (wi), divided by the amount of change in the degree of branching b _i per the elution temperature interval _{5 ℃ (b i -b i-} 1) The concentration c _i is obtained, the relative concentration is plotted against the branching degree, and the composition distribution curve is obtained. This composition distribution curve is divided with a constant width, and Cb is calculated by the following formula [III].

(Equation 3) Here, c _j and b _j are the relative concentration and the degree of branching of the j-th fraction, respectively. Cb is 1.0 when the composition of the sample is uniform, and increases as the composition distribution spreads.

Many proposals have been made for the method of describing the composition distribution of the ethylene / α-olefin copolymer. For example, in JP-A-60-88016, numerical processing is performed assuming that the cumulative weight fraction has a specific distribution (logarithmic normal distribution) with respect to the number of branches of each separated sample obtained by separating the sample from the solvent. And the weight average branching degree (Cw)
And the number average branching degree (Cn). The approximation calculation accuracy is lowered when the number of branches and cumulative weight fraction of the sample away from the lognormal distribution, for example, a correlation coefficient R ² to perform measurements on commercially available LLDPE is fairly low, the accuracy is insufficient. Cb of the present invention has a different definition and measurement method from Cw / Cn.

The amount (X,% by weight) of the ODCB-soluble component at 25 ° C. of the ethylene / α-olefin copolymer (A) used in the present invention is determined by the high branching component contained in the ethylene / α-olefin copolymer. And the content ratio of the low molecular weight component, which causes reduction of heat resistance and stickiness of the surface of the molded product, and therefore is preferably small.
On the other hand, X has a correlation with the α-olefin content and average molecular weight of the entire copolymer, and thus with the density (d) and MFR. In the present invention, the values of d and MFR are d−0.008 × log [MFR] ≧ 0.93.
When the relation of is satisfied, X is appropriately less than 2% by weight, preferably less than 1% by weight, more preferably 0.5.
% By weight. Also, the values of d and MFR are d-
When 0.008 × log [MFR] <0.93 is satisfied, X <9.8 × 10 ³ × (0.9300−d + 0.008)
The range of X satisfying the relation of xlog [MFR]) ² +2.0 is suitable, and preferably X <7.4 × 10 ³ x (0.930).
0-d + 0.008 × log [MFR]) ² +1.0, more preferably X <5.6 × 10 ³ × (0.9300-d +
This is a range that satisfies the relationship of 0.008 × log [MFR]) ² +0.5. The fact that d, MFR and X satisfy the above relationship indicates that the amount of the highly branched component is not excessive, that is, the α-olefin contained in the entire copolymer is not ubiquitous.

The amount (X) of the ODCB-soluble component at 25 ° C. is measured by the following method. That is,
0.5 g of the sample is added to 20 ml of ODCB, heated at 135 ° C. for 2 hours to completely dissolve the sample, and then cooled to 25 ° C. After leaving this solution at 25 ° C. overnight, it is filtered through a Teflon filter to collect the filtrate. Using the filtrate as a sample solution, the intensity of the absorption peak near the wave number 2925 cm ⁻¹ due to the asymmetric stretching vibration of methylene is measured by an infrared spectroscope, and the sample concentration in the filtrate is calculated from the calibration curve prepared in advance. X is calculated from this value.

The ethylene / α-olefin copolymer (A) used in the present invention shows a plurality of peaks in the elution temperature-elution amount curve (TREF curve) determined by the continuous temperature rising elution fractionation method (TREF). The peak on the high temperature side is particularly preferably present between 85 ° C and 100 ° C. Those having such a peak have a high melting point and a high degree of crystallinity, and therefore a molded product using the same has excellent heat resistance and rigidity.

The method of measuring TREF used in the present invention is as follows. Samples with heat stabilizers and sample concentrations of 0.
It is added to ODCB so as to be 05% by weight, and dissolved by heating at 135 ° C. After pouring 5 ml of this heated solution into a column filled with glass beads, it is cooled to 25 ° C. at a cooling rate of 0.1 ° C./min to deposit a sample on the surface of the glass beads. Next, while flowing ODCB at a constant flow rate through this column, the column temperature is raised at a constant rate of 50 ° C./hr to sequentially elute the sample soluble in the solution at each temperature.
At this time, the wave number 2925 due to the asymmetric stretching vibration of methylene
The elution temperature-IR absorption curve can be obtained by continuously measuring the absorption at cm ⁻¹ with an infrared detector.
Further, the elution temperature-elution amount curve can be obtained by obtaining the sample concentration in the filtrate from the calibration curve prepared in advance. T
According to the REF analysis, the change in the elution rate with respect to the temperature change can be continuously measured with a very small amount of sample,
It is possible to detect relatively fine peaks that cannot be detected by the fractionation method. Ethylene / α- with multiple peaks in Figure 1
An example of the elution temperature-IR absorption curve of the olefin copolymer (A) is shown, and for comparison, an example of the elution temperature-IR absorption curve of the copolymer with a so-called metallocene catalyst is shown in FIG.

The specific ethylene / α-olefin copolymer (A) used in the present invention may be any one satisfying the above-mentioned properties (a) to (e) to (f), such as a Ziegler catalyst and a Phillips catalyst. It is possible to polymerize with a metallocene catalyst or the like, but it is preferable to use a catalyst obtained by bringing the following components (C ₁ ) to (C ₅ ) into contact with each other. (C ₁ ): a compound represented by the general formula Me ¹ R ¹ _p (OR ² ) _q X ¹ _4-pq (wherein Me ¹ represents Zr, Ti or Hf, and R ¹
And R ² is a hydrocarbon group having 1 to 24 carbon atoms, X ¹ is a halogen atom, and p and q are integers satisfying the relationships of 0 ≦ p <4, 0 ≦ q <4, and 0 ≦ p + q ≦ 4. ) (C ₂ ): a compound represented by the general formula Me ² R ³ _m (OR ⁴ ) _n X ² _zmn (wherein Me ² is an element of Group I to III of the periodic table, R ³
And R ⁴ is a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom or a hydrogen atom (provided that X ² is a hydrogen atom only when Me ² is a Group III element of the periodic table). Where z is the valence number of Me ² , and m and n are 0 ≦ m ≦.
z, an integer satisfying the relations of 0 ≦ n ≦ z and 0 ≦ m + n ≦ z) (C ₃ ): an organic cyclic compound having a conjugated double bond (C ₄ ): obtained by reacting an organoaluminum compound with water modified organoaluminum compound containing Al-O-Al bonds to be (C _5): inorganic carrier and / or particulate polymer carrier

The above general formula of the catalyst component (C ₁ ) Me ¹ R ¹ _p (O
In the compound represented by R ² ) _q X ¹ _4-pq , Me ¹ in the formula
Represents Zr, Ti or Hf as described above. These transition metals are not limited to one type, and a plurality of types can be used, but it is particularly preferable that Zr is contained in the point that a copolymer having excellent weather resistance can be obtained. R ¹ and R ² are hydrocarbon groups having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group. Groups, alkyl groups such as butyl groups; alkenyl groups such as vinyl groups and allyl groups; aryl groups such as phenyl groups, tolyl groups, xylyl groups, mesityl groups, indenyl groups, naphthyl groups; benzyl groups, trityl groups, phenethyl groups, Examples thereof include an aralkyl group such as a styryl group, a benzhydryl group, a phenylbutyl group and a neophyl group. These may have branches. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p and q satisfy the relationships of 0 ≦ p <4, 0 ≦ q <4 and 0 ≦ p + q ≦ 4.

Examples of the compound of the above catalyst component (C ₁ ) are tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium, tetrabutoxyzirconium, tributoxymonochlorozirconium. , Dibutoxydichlorozirconium, tetrabutoxytitanium, tetrabutoxyhafnium, and the like, and two or more kinds of these may be mixed and used.

The above catalyst component (C ₂ ) has the general formula Me ² R ³ _m (O
In the compound represented by R ⁴ ) _n X ² _zmn , Me ² in the formula
Represents an element of groups I to III of the periodic table, and specifically, lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum and the like. R ³ and R ⁴ are hydrocarbon groups having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms,
Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group And an aralkyl group such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neofuyl group. These may have branches. X ² represents a halogen atom or a hydrogen atom such as fluorine, iodine, chlorine and bromine. However, X ² is a hydrogen atom only when Me ² is a Group III element of the periodic table exemplified by boron, aluminum and the like. Z represents the valence number of Me ² , and m and n are 0 ≦ m ≦ z, 0 ≦ n ≦ z and 0 ≦ m.
It is an integer that satisfies the relationship of + n ≦ z.

Examples of the above-mentioned catalyst component (C ₂ ) compounds include organolithium compounds such as methyllithium and ethyllithium; organomagnesium compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride and ethylmagnesium chloride; dimethylzinc, Organozinc compounds such as diethylzinc; Organoboron compounds such as trimethylboron and triethylboron; Trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum,
Examples thereof include derivatives of organic aluminum compounds such as tridecyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide and diethyl aluminum hydride.

The organic cyclic compound having a conjugated double bond of the catalyst component (C ₃ ) is one ring having two or more conjugated double bonds, preferably 2 to 4 and more preferably 2 to 3. Have 1 or 2 or more and have a total carbon number of 4 to 2
4, preferably 4 to 12 cyclic hydrocarbon compounds; wherein the cyclic hydrocarbon compounds are partially 1 to 6 hydrocarbon residues (typically, alkyl groups or aralkyl groups having 1 to 12 carbon atoms) A cyclic hydrocarbon compound substituted with; a ring hydrocarbon having two or more, preferably 2 to 4, more preferably 2 to 3 rings having a conjugated double bond and having a total carbon number of 4 to 24, preferably an organosilicon compound having a cyclic hydrocarbon group of 4 to 12; wherein the cyclic hydrocarbon group is partially substituted with 1 to 6 hydrocarbon residues or an alkali metal salt (sodium or lithium salt) Other examples include organic silicon compounds. Those having a cyclopentadiene structure in the molecule are particularly desirable.

Suitable compounds of the above catalyst component (C ₃ ) include cyclopentadiene, indene, azulene or derivatives thereof with a substituent such as alkyl, aryl, aralkyl, alkoxy or aryloxy. Further, a compound in which these compounds are bonded (crosslinked) via an alkylene group (having a carbon number of usually 2 to 8, preferably 2 to 3) is also suitably used.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. A _L SiR _4-L Here, A represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, the cyclic hydrocarbon group exemplified by the substituted indenyl group, and R represents a methyl group, an ethyl group, Alkyl groups such as propyl group, isopropyl group, butyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group; aryl groups such as phenyl group; aryloxy groups such as phenoxy group; aralkyl groups such as benzyl group Represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 12 or hydrogen, L
Is in the range of 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound as the catalyst component (C ₃ ) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,
Carbon number 5 such as 3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7-dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene and methylfluorene. 24 cyclopolyene or substituted cyclopolyene; monocyclopentadienylsilane, biscyclopentadienylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, trisindenylsilane and the like.

The modified organoaluminum compound containing an Al--O--Al bond obtained by reacting the organoaluminum compound of the catalyst component (C ₄ ) with water is obtained by reacting an alkylaluminum compound with water. , Is a modified organoaluminum usually called aluminoxane, and is usually 1 to 100, preferably 1 to 1 in a molecule.
It contains 50 Al-O-Al bonds. The modified organoaluminum compound may be linear or cyclic.

In the above, the reaction between the organic aluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene,
Alicyclic or aromatic hydrocarbons are preferred. The reaction ratio of water and the organoaluminum compound (water / Al molar ratio) is usually 0.25 / 1 to 1.2 / 1, preferably 0.5 / 1 to 1 /.
It is one.

Examples of the inorganic carrier and / or the particulate polymer carrier of the catalyst component (C ₅ ) include carbonaceous materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof, or thermoplastic resins, Thermosetting resin etc. are mentioned. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , Ti
_{O 2, B 2 O 3,} CaO, ZnO, BaO, ThO 2 and the like or mixtures thereof, and _{SiO 2 -Al 2 O 3, SiO} 2 -V 2 O
₅ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —MgO,
Examples thereof include SiO ₂ —Cr ₂ O ₃ . Among these,
Those containing at least one selected from ₂ and Al ₂ O ₃ as a main component are preferable. Further, as the organic compound used for the particulate polymer carrier, either a thermoplastic resin or a thermosetting resin can be used, and specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, polyacrylic. Examples thereof include methyl acidate, polymethylmethacrylate, polystyrene, polynorbornene, various natural polymers, and mixtures thereof.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are treated with an organoaluminum compound or a modified organoaluminum compound containing an Al--O--Al bond. To be used after contacting with.

As a method for producing the ethylene / α-olefin copolymer (A) used in the present invention, any of a gas phase method, a slurry method, a solution method and the like can be used, and a one-step polymerization method, a multi-step polymerization method and the like can be used. Any one may be used, and it is not particularly limited.

The first of the other olefinic polymers (B) used in the present invention is to use a Ziegler type catalyst or Phillips catalyst etc. by a conventional ionic polymerization method (hereinafter collectively referred to as "Ziegler type catalyst"). The ethylene polymer obtained is preferably a density of 0.86 to 0.95 g / cm ^3.
Ethylene / α-olefin copolymer (B ₁ ) of, for example, linear medium density polyethylene (MDPE),
Examples include linear low density polyethylene (LLDPE) and ultra-low density polyethylene (VLDPE).

The linear medium density polyethylene and linear low density polyethylene (MDPE and LLDPE) are
The density is in the range of 0.91 to 0.95 g / cm ³ , preferably 0.91 to 0.94 g / cm ³ (LLDPE),
MFR is 0.1 to 20 g / 10 minutes, preferably 0.5 to 15 g /
It is selected from the range of 10 minutes, more preferably 0.7 to 10 g / 10 minutes. The melt tension is 0.3 to 5.0 g, preferably 0.4 to 4.0 g, and more preferably 0.5 to 3.5 g. The molecular weight distribution (Mw / Mn) is 2.5 to 5, preferably 3 to 4.5. In addition, Mw / Mn is the weight average molecular weight / number average molecular weight by GPC analysis.

Ultra low density polyethylene (VLDPE)
Means a density of 0.86 to 0.91 g / cm ³ , preferably 0.8.
Is a 8~0.905g / cm ^3, MFR is 0.1~20g / 10
Min, preferably 0.5-10 g / 10 min. VLDPE has an intermediate property between LLDPE and ethylene / α-olefin copolymer rubber (EPR, EPDM, etc.), and preferably has a density of 0.86 to 0.91 g /
specific ethylene having a property of cm ³ , a maximum melting point (Tm) by differential scanning calorimetry (DSC) of 60 ° C. or higher, and preferably boiling n-hexane insoluble content of 10 wt% or higher.
It is an α-olefin copolymer. Polymerized by using a catalyst composed of a solid catalyst component containing at least titanium and / or vanadium and an organoaluminum compound,
A resin having both a highly crystalline portion of LDPE and an amorphous portion of an ethylene / α-olefin copolymer rubber, and the mechanical characteristics and heat resistance, which are the characteristics of the former,
The latter features, such as rubber-like elasticity and low temperature impact resistance, coexist in a well-balanced manner.

The α-olefin of the ethylene / α-olefin copolymer (B ₁ ) has a carbon number of 3 to 12, preferably 3 to 10, specifically, propylene, butene-1, 4-methylpentene-1, hexene-
1, octene-1, decene-1, dodecene-1 and the like. The content of these α-olefins is
It is preferable to select from the range of 3 to 40 mol%.

The second of the other olefinic polymers (B) used in the present invention is low density polyethylene by high pressure radical polymerization, ethylene / vinyl ester copolymer, and ethylene and α, β-unsaturated carboxylic acid or Examples thereof include a copolymer (B ₂ ) with the derivative.

The above low density polyethylene (LDPE) is
MFR of 0.1 to 20 g / 10 minutes, preferably 0.5 to 15 g /
It is 10 minutes, more preferably 1.0 to 10 g / 10 minutes. M
If FR is within this range, the melt tension of the composition will be in an appropriate range. The density is 0.91 to 0.94 g / cm ³ , preferably 0.912 to 0.935 g / cm ³ , and more preferably 0.912 to 0.930 g / cm ³ , and the melt tension is 1.5 to 1.5.
25 g, preferably 3 to 20 g, more preferably 3 to
It is 15 g. The melt tension is a physical property showing the elasticity of the resin, and the film can be easily formed within the above range.
The Mw / Mn is 3.0 to 10, preferably 4.0 to 8.
0.

The above ethylene / vinyl ester copolymer means ethylene and vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, trifluoro, produced by a high pressure radical polymerization method. It is a copolymer with vinyl ester monomers such as vinyl acetate. Among these vinyl esters, vinyl acetate can be mentioned as a particularly preferable one. As the ethylene / vinyl ester copolymer, ethylene is 50 to 99.5% by weight, and vinyl ester is 0.1.
5 to 50% by weight, other copolymerizable unsaturated monomer 0 to 4
A copolymer consisting of 9.5% by weight is preferred. The vinyl ester content is in the range of 3 to 20% by weight, preferably 5 to 15% by weight. The MFR of these copolymers is 0.1 to 2
It is 0 g / 10 minutes, preferably 0.3-10 g / 10 minutes, and the melt tension is 2.0-25 g, preferably 3-20 g.

Typical examples of the copolymer of ethylene with an α, β-unsaturated carboxylic acid or its derivative include a copolymer of ethylene with acrylic acid or methacrylic acid or their alkyl esters. .
Examples of alkyl esters of acrylic acid and methacrylic acid include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate,
Isopropyl methacrylate, -n-butyl acrylate,
Examples thereof include -n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate and glycidyl methacrylate. Of these, particularly preferred are methyl or ethyl esters of acrylic acid and methacrylic acid. The content of acrylic acid ester or methacrylic acid ester is in the range of 3 to 20% by weight, preferably 5 to 15% by weight. The MFR of these copolymers is 0.1-
It is 20 g / 10 minutes, preferably 0.3 to 10 g / 10 minutes, and the melt tension is 2.0 to 25 g, preferably 3 to 20 g.

The blending ratio of the component (A) and the component (B) is 100 to 20% by weight of the component (A), and 80% by weight or less, preferably 50% by weight or less of the component (B). In particular, when importance is attached to the adhesive strength of the longitudinal and transverse fibers, the low temperature heat sealability, etc., it is preferable to use the component (A) as a main component. When the properties and economy are also taken into consideration, the component (B) can be blended up to 80% by weight. When the content of the component (A) is less than 20% by weight and the content of the component (B) exceeds 80% by weight, characteristics such as adhesive strength of longitudinal and transverse fibers and low temperature heat sealability may not be exhibited. Occurs.

The uniaxially oriented body in the first invention of the present application includes a uniaxially oriented film, a uniaxially oriented network, a uniaxially oriented tape, a flat yarn and the like. These uniaxially oriented materials may be used alone or in a laminate of a plurality of them, depending on the purpose or application, and may be laminated by intersecting the orientation axes.

The nonwoven fabric or woven fabric according to the second invention of the present application is a uniaxially oriented body having a multilayer structure consisting of a thermoplastic resin layer (I) and an adhesive layer (II), which has a longitudinal uniaxially oriented reticulated film (a) and a lateral direction. It is formed by selecting at least one kind from the uniaxially oriented network film (b) and the uniaxially oriented multilayer tape (c), and laminating or weaving them so that the orientation axes cross each other through the adhesive layer (II) of the uniaxially oriented body. .

The orientation magnification of the uniaxially oriented body is 1.1 to 1
5, preferably selected from the range of 3 to 10. If the orientation magnification is less than 1.1, the mechanical strength of the oriented body is not sufficient.
On the other hand, if the orientation magnification exceeds 15, it is difficult to perform orientation by a normal method, and a problem such as requiring an expensive device arises.

The method of orientation in the present invention includes a rolling method or a stretching method. In the stretching method, a roll stretching method (free uniaxial stretching method), a hot plate stretching method, a cylinder stretching method, a hot air stretching method is used. Etc. can be used. The free uniaxial stretching method is particularly preferable. With the free uniaxial stretching method,
This is a method in which the stretching distance (distance between the low speed roll and the high speed roll) is made sufficiently long with respect to the width of the thermoplastic resin film, and the film is stretched while freely shrinking in the width direction.

The rolling method referred to in the present invention is that the thermoplastic resin film is passed between two heating rolls having a gap smaller than its thickness, and the melting point (softening point) of the resin film is set.
It refers to a method of pressing at a lower temperature to extend the length by a rate at which the thickness is reduced.

Thermoplastic resin layer (I) of the above multilayer film
The thickness ratio between the adhesive layer and the adhesive layer (II) is not particularly limited,
Generally, the adhesive layer (II) is 5 times the total thickness of the multilayer film.
It is preferably 0% or less, preferably 40% or less in order to maintain mechanical strength and the like. The thickness of the thermoplastic resin layer (I) of the oriented multilayer film or tape is preferably about 20 to 100 μm. Further, if the thickness of the adhesive layer (II) is 3 μm or more, the required physical properties such as the adhesive strength at the time of heat fusion are satisfied, but it is usually selected from the range of 3 to 60 μm, preferably 5 to 40 μm.

In addition, the melting point of the resin of the adhesive layer (II) and the melting point of the resin of the thermoplastic resin layer (I) have a temperature difference of 5 ° C. or more, particularly 10 to 50 ° C. or more. Also, in order to maintain mechanical strength, it is preferable.

In the present invention, it is essential to add an additive to the thermoplastic resin layer (I) as the inner layer in order to obtain a non-woven fabric or a woven fabric imparted with functions such as coloring and weather resistance without any trouble. . By thus blending the additive into the thermoplastic resin layer (I) as the inner layer, the stain on the die lip during film formation is drastically reduced, and the frequency of cleaning is reduced.
Further, even at the time of fiber splitting, the amount of additive powder, resin, etc. accumulated in the splitter part as eye blemishes is small, and the frequency of the removal work is reduced. Conventionally, when dirt is increased, the teeth of the splitter are clogged with these dirt, the teeth cannot be cut, and there are many vertical cracks in the orientation film and irregular cracks in the splitting process, and a regularly arranged mesh is formed. There are problems such as not being able to obtain it. In addition, a large amount of impurities are mixed into the product from such stains, and the irregularity of the non-woven fabric mesh not only lowers the product value, but also leads to lower strength of the non-woven fabric. By using the present invention, these problems are solved.
As the additive, a light resistance agent, an ultraviolet absorber, a colorant,
Examples thereof include pigments and inorganic fillers.

The light stabilizer is a benzotriazole type,
It is an ultraviolet absorber and a light stabilizer composed of various compounds such as a benzophenone derivative, a substituted acrylonitrile type, a salicylic acid type, a nickel complex salt type and a hindered amine type.

Examples of the benzotriazole-based UV absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-
tert-butylphenyl) benzotriazole, alkylated hydroxybenzotriazole and the like.

As the ultraviolet absorber of the benzophenone derivative, 2-hydroxy-4-methoxybenzophenone,
2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 4-dodecyloxy-
2-hydroxybenzophenone etc. are mentioned.

Examples of the acrylonitrile-based ultraviolet absorber include 2-ethyl-hexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate.

Examples of salicylic acid type ultraviolet absorbers include phenyl salicylate, p-tert-butylphenyl salicylate and p-octylphenyl salicylate.

As the nickel complex salt type ultraviolet absorber,
Nickel-bis (octylphenyl sulfide),
[2,2′-thio-bis (4-tert-octylphenolate)]-n-butylamine nickel and the like can be mentioned.

As the hindered amine-based light stabilizer,
Examples thereof include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. Among the various light stabilizers described above, the hindered amine light stabilizer is most preferable.

The amount of the light-proofing agent varies depending on the use, operating environment, purpose, etc. of the non-woven fabric or woven fabric, and the required amount may be appropriately blended. Preferably 300 to 10,000
It is desirable to blend in the range of ppm. If the blending amount is less than 300 ppm, the duration of light resistance may be short or the effect may not be exhibited. 10,000 pp
If it exceeds m, the duration of light resistance becomes longer,
This is not desirable because it increases costs.

As the colorant or pigment in the present invention, organic pigments and inorganic pigments are used. Examples of the organic pigment include azo-based, anthraquinone-based, phthalocyanine-based, quinacridone-based, isoindolinone-based, dioxane-based, perylene-based, quinophthalone-based, and perinone-based pigments. In addition to food yellow No. 4 (tartrazine), food yellow No. 5 (sunset yellow FCF), food green No. 3 (fast green FCF), copper chlorophyll, and sodium iron chlorophyllin registered in Usual pigments used, for example, organic pigments such as phthalocyanine blue, phthalocyanine green, fast yellow and diazo yellow can be appropriately used. Further, as the inorganic pigment, titanium dioxide, lead white, zinc white,
Examples thereof include white pigments such as lithopone, barite, precipitated barium sulfate, calcium carbonate, gypsum and precipitated silica, and cadmium sulfide, cadmium selenide, ultramarine blue, iron oxide, chromium oxide, carbon black and the like.

As the antioxidant in the present invention, it is possible to use an ordinary antioxidant, but phenol-based, phosphorus-based and sulfur-based antioxidants are particularly preferable. As the phenolic antioxidant, a hindered phenolic compound is used, specifically, 2,2 '
-Methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert
-Butylphenol), 4,4'-thiobis (3-methyl-
6-tert-butylphenol), tetrakis [methylene 3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate] methane, n-octadecyl 3
-(4'-Hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, 2,4-bisoctylthio-6-
(4'-Hydroxy-3 ', 5'-di-tert-butylanilino) -1,3,5-triazine, 1,3,5-tris (4'-
Hydroxy-3 ', 5'-di-tert-butylbenzyl)-
1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (3'-hydroxy-2 ', 6'
-Dimethyl-4'-tert-butylbenzyl) -1,3,5-
Triazine-2,4,6 (1H, 3H, 5H) -trione,
1,3,5-trimethyl-2,4,6-tris (4'-hydroxy-3 ', 5'-di-tert-butylbenzyl) benzene and the like can be mentioned.

As the phosphorus antioxidant, compounds such as phosphite, phosphonite and phosphaphenanthrene are used. Specifically, dioctadecyl pentaerythrityl diphosphite, trioctadecyl phosphite and tris are used. (Nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite,
Examples thereof include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite and the like.

As the sulfur antioxidant, thiol, sulfide, etc. are used. Specifically, 3,3 '
-Thiodipropionic acid, didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, pentaerystyryl tetrakis (3-dodecyl thiopropionate), pentaerythrityl tetrakis (3
-Octadecyl thiopropionate) and the like.

These antioxidants are generally used in an amount of 0.02 to 1.0 part by weight, preferably 0.0 to 100 parts by weight of the resin.
It is used in the range of 3 to 0.5 parts by weight. Compounding amount is 0.02
If it is less than 10 parts by weight, the antioxidant effect is not exhibited, and it is 1.0
Greater effects cannot be expected even if the amount used exceeds parts by weight. The antioxidant and the ultraviolet absorber may be used either individually or in combination of two or more. In particular, it is preferable to combine a phenol-based antioxidant and a phosphorus-based antioxidant because the effect is dramatically improved. That is, by using these in combination, it is possible to prevent the deterioration of the resin due to heat during the extrusion process, the change with time of the hue due to ultraviolet rays, and the fading. Therefore, it is desirable to use the pigment and the like together from the initial stage.

Typical examples of the light-shielding agent include aluminum powder and the like. The above-mentioned film to which aluminum powder is added is effective in reflecting light and protecting and growing crops and the like, but it is generally known that it has a function of promoting photodegradation of the resin. Similarly, pigments and the like also have the action of promoting photodegradation. By using the light-proofing agent, or a light-proofing agent and a phenol-based, phosphorus-based, or sulfur-based antioxidant, a light-shielding agent, a pigment or the like can significantly suppress the action of promoting the photodegradation of the surface layer, Since a synergistic effect is also exerted on weather resistance, it is desirable to use a light resistance agent and an antioxidant together.

In the non-woven fabric and woven fabric of the present invention, the uniaxially oriented reticulated film (a), the uniaxially oriented reticulated film (b) and the uniaxially oriented film having a multilayer structure composed of the thermoplastic resin layer (I) and the adhesive layer (II) are used. At least one kind of uniaxially oriented body selected from the oriented multilayer tape (c) is laminated or woven through the adhesive layer (II) so that the orientation axes intersect. Hereinafter, these non-woven fabrics and woven fabrics will be described in detail with reference to the drawings.

FIG. 3 is a perspective view of a longitudinal uniaxially oriented network film (a) obtained by uniaxially orienting a multilayer film in the length direction and splitting (splitting), which is an embodiment of the present invention.
In the figure, a longitudinally uniaxially oriented reticulated film 1 has an adhesive layer (II) 3 containing a specific ethylene / α-olefin copolymer on both surfaces of a thermoplastic resin layer (I) 2 uniaxially oriented in the length direction of the film. They are laminated and consist of trunk fibers 4 and branch fibers 5.

FIG. 4 is a perspective view of a laterally uniaxially oriented reticulated film (b) in which a multilayer film is slit and oriented uniaxially in the lateral direction, which is an embodiment of the present invention. In the figure, the horizontal uniaxially oriented reticulated film 6 has a specific ethylene / α-olefin copolymer on both sides of the thermoplastic resin layer (I) 2 uniaxially oriented at right angles (transverse direction) to the length direction of the film. The adhesive layer (II) 3 including is laminated.

The uniaxially oriented multi-layer tape (c) is a multi-layer film having two or more layers produced by extrusion molding such as a multi-layer inflation method and a multi-layer T-die method. It is uniaxially oriented in 1.1 to 15, preferably 3 to 10. FIG. 5 is a perspective view of a uniaxially oriented multilayer tape (c) which is an embodiment of the present invention. In the figure, a uniaxially oriented multilayer tape 7 is an adhesive layer (II) containing a specific ethylene / α-olefin copolymer on both surfaces of a uniaxially oriented thermoplastic resin layer (I) 2 as in the above-mentioned oriented network film. 3 is a laminated tape.

The non-woven fabric or woven fabric of the present invention is obtained by laminating or weaving at least one kind of the uniaxially oriented body described above so that the orientation axes cross each other through the adhesive layer (II). The specific combination of the uniaxially oriented body is as follows: (1) Two longitudinal uniaxially oriented network films (a) shown in FIG. 6 are laminated (a /
a) The laminated non-woven fabric (A), (2) the longitudinal uniaxially oriented reticulated film (a) and the lateral uniaxially oriented reticulated film (b) are laminated (a /
b) Non-woven fabric (B), (3) Non-woven fabric (C), (4) in which two sets (c / c) of uniaxially oriented multilayer tapes (c) shown in Fig. 7 are laminated.
Woven fabric (D) obtained by weaving the uniaxially oriented multilayer tape (c) shown in FIG. 8, (5) Nonwoven fabric (A) / Nonwoven fabric (B) (hereinafter, (A /
Abbreviated as B), etc.), (A / C) or (A / D)
Non-woven fabric consisting of the laminated structure of (6) (B / C) or (B / C)
D) non-woven fabric, (7) (C / D) non-woven fabric, (8) (a / C) or (a / D) non-woven fabric, (b / C / b) or (b / D /
b) non-woven fabric, (9) (C / a / C) or (C / b / C) non-woven fabric, (D / a / D) or (D / b / D) non-woven fabric, (1
0) Nonwoven fabric of (A / C / A) or (A / D / A), (B / C /
B) or (B / D / B) non-woven fabric, (11) (A / C / B) or (A / D / B) non-woven fabric, and the like.

FIG. 9 is a schematic view showing a method for producing a longitudinally uniaxially oriented network film (a) which is an embodiment of the present invention.
As shown in FIG. 9, the longitudinal uniaxially oriented reticulated film (a) is
Mainly (1) multilayer film forming step, (2) multilayer film orientation step, (3) split step of splitting the oriented multilayer film parallel to the orientation axis, and (4) winding step of winding the split film. Is manufactured through.

Each step will be described below. In FIG.
(1) In the step of forming a multilayer film, the main extruder 11 is supplied with the thermoplastic resin used for the highly oriented resin layer (I) such as high density polyethylene or polypropylene, and the two auxiliary extruders 12 and 12 are used. Adhesive layer resin with specific ethylene / α
-Supplying the olefin copolymer or a mixture thereof, the thermoplastic resin extruded from the main extruder 11 is used as the central layer (orientation layer), and the adhesive layer resin extruded from the two auxiliary extruders 12 and 12 is used. As an inner layer and an outer layer, a multilayer film is produced by inflation molding. FIG. 9 shows an example of the case where three extruders are used to form a film by downward blowing water-cooled inflation 14 through a multilayer annular die 13.
As a method for producing the multilayer film, a multilayer inflation method, a multilayer T-die method, or the like can be used and is not particularly limited. Among these molding methods, the water-cooled inflation method is preferable because it has advantages such as being capable of rapidly cooling a thick film and maintaining transparency.

(2) In the orientation step, the above-mentioned formed annular multilayer film is cut into two films F and F ', which are passed through an oven 15 equipped with an infrared heater, a hot air blower, etc. to a predetermined temperature. While heating, roll orientation is performed at an orientation magnification of 1.1 to 15, preferably 5 to 12, and more preferably 6 to 10 with respect to the initial dimension. The orientation temperature is not higher than the melting point of the thermoplastic resin of the central layer, and is usually 20 to 16
0 ° C., preferably 60 to 150 ° C., more preferably 9
It is in the range of 0 to 140 ° C., and it is preferable to carry out in multiple stages.

(3) In the split (splitting) step, the oriented multilayer film is brought into sliding contact with a splitter (rotary blade) 16 rotating at a high speed, and the film is subjected to splitting (splitting). As the split method, in addition to the above, a mechanical method such as a method of beating a multilayer uniaxially oriented film, a method of twisting, a method of sliding rubbing (rubbing), a method of brushing, or an air jet method, an ultrasonic method, or a laser. Innumerable fine cuts may be formed by a method or the like. Among these, the rotary mechanical method is particularly preferable. Examples of such rotary mechanical methods include various types of splitters such as a tap screw type splitter, a file-shaped rough surface splitter, and a needle roll type splitter. For example, as the tap screw type splitter, one having a pentagonal or hexagonal shape and having 10 to 40, preferably 15 to 35, threads per inch is usually used. Further, as the file-like rough surface splitter, the one described in Japanese Utility Model Publication No. 51-38980 is suitable. The file-like rough surface splitter is
The surface of the circular cross-section shaft is processed into a round file for ironwork or a rough surface body similar to this, and two spiral grooves are provided at equal pitches on the surface. Specific examples of these are:
U.S. Pat. Nos. 3,662,935 and 3,693,851
And the like disclosed in No.

The method for producing the reticulated film is not particularly limited, but preferably, a splitter is arranged between the nip rolls, moved while applying tension to the multilayer uniaxially oriented film, and brought into sliding contact with the splitter rotating at a high speed. There is a method of splitting and reticulating.

The moving speed of the film in the above split step is usually 1 to 1,000 m / min, preferably 10
It is 500 m / min. The rotational speed (peripheral speed) of the splitter can be appropriately selected depending on the physical properties of the film, the moving speed, the properties of the target reticulated film, etc., but usually 10 to 3,000 m / min, preferably 50 to
It is 1,000 m / min.

The longitudinally uniaxially oriented reticulated film (a) thus formed by splitting is widened as desired, and then heat treated 1.
In (4) winding step 18, after passing through 7, it is wound into a predetermined length and supplied as a non-woven fabric original fabric.

FIG. 10 is a schematic view showing a process for producing a nonwoven fabric (A) in which two longitudinally uniaxially oriented network films (a) of the present invention are laminated (a / a). In FIG. 10, the longitudinal uniaxially oriented reticulated film (a) 110 (hereinafter, referred to as “longitudinal web”) manufactured as described above is unrolled from a material roll unrolling roll and run at a predetermined feeding speed to perform a widening step 111. And a widening machine (No. 4-35154, No. Heihei, not shown) for several times widening, and heat treatment is performed if necessary. Another vertical uniaxially oriented reticulated film (a) 210 (hereinafter, referred to as "horizontal web") is fed out from a raw fabric feeding roll in the same manner as the vertical web, and is fed at a predetermined feeding speed to be fed to a widening step 211 to be widened by a widening machine. (The same as in the case of a vertical web), the width is expanded several times, and if necessary, a heat treatment is performed, and then the length is cut into a length equal to the width of the vertical web 110, the vertical web is fed from a direction perpendicular to the running film, and laminated. In step 112, the latitudinal and latitudinal layers are conveyed via the adhesive layer (II) so that the orientation axes are orthogonal to each other. In the thermocompression bonding step 113, heat fusion is performed by a thermal cylinder at a temperature not higher than the melting point of the oriented central thermoplastic resin layer (I) and not lower than the melting point of the adhesive layer (II), and the product history in the winding step 114. It is taken up as a laminated nonwoven fabric.

FIG. 11 is a schematic diagram showing a process for producing a nonwoven fabric (B), which is an embodiment of the present invention, in which a longitudinally uniaxially oriented network film (a) and a laterally uniaxially oriented network film (b) are laminated (a / b). Is. As shown in FIG. 11, mainly, (1) a multilayer film forming step, (2) a slit step of performing a slitting treatment at right angles to the longitudinal direction of the multilayer film, (3) a lateral uniaxial orientation step of the multilayer slit film, and (4) It includes a pressure-bonding step in which a vertical web is laminated on a horizontally uniaxially oriented slit film and thermocompression bonding is performed.

Each step will be described below. In FIG.
(1) In the step of forming a multilayer film, a thermoplastic resin used for the resin layer (I) is supplied to the main extruder 311 and a specific ethylene / α-olefin copolymer as an adhesive layer resin or a sub-extruder 312 is supplied. Feeding the mixture, the main extruder 3
Using the thermoplastic resin extruded from No. 11 as the inner layer and the adhesive layer resin extruded from the sub-extruder 312 as the outer layer, a two-layer film is produced by inflation molding. FIG.
In the above, an example is shown in which two extruders are used to form a film by downward blowing water cooling inflation 314 through a multilayer annular die 313. As a method for producing a multilayer film,
Similar to the example of FIG. 9, a multilayer inflation method, a multilayer T-die method, or the like can be used, and there is no particular limitation.
Among these molding methods, the water-cooled inflation method is preferable because it has advantages such as being capable of rapidly cooling a thick film and maintaining transparency and the like. Inflation-molded film can be used as is between rolls.
A sheet having a three-layer structure of an adhesive layer (II) / thermoplastic resin layer (I) / adhesive layer (II) is obtained by crushing after fine orientation as desired, and for a vertical film in the example of FIG. 9 described above. Since three extruders can be omitted to two, the economical effect is great.

(2) In the slitting step, the film-formed annular multilayer film is pinched and flattened, and then finely oriented by rolling to form a three-layered film, which is perpendicular to the traveling direction and staggered. Insert the lateral slit 315. Examples of the slitting method include a method of slitting with a sharp blade edge such as a razor blade or a high-speed rotary blade, a method of forming a slit with a score cutter, a shear cutter, and the like, but particularly a slitting method with a hot blade (heat cutter). Is most preferred. As an example of such a hot blade, Japanese Patent Publication No. 61-11757, U.S. Pat. No. 4,489,
No. 630, No. 2,728,950 and the like. The slitting method with a hot blade has the effect of raising the edge of the cut edge of the film that has been finely oriented by rolling in the preceding stage,
It is possible to prevent the cut from tearing and propagating during the orientation in the subsequent lateral orientation step.

(3) In the orientation step, the film subjected to the slit treatment is subjected to lateral orientation 316. Examples of the lateral orientation method include a tenter method and a pulley method, but the pulley method is preferable because the apparatus is small and economical. Examples of the pulley method include the methods disclosed in British Patent No. 849,436 and Japanese Patent Publication No. 57-30368. The conditions such as the orientation temperature are the same as in the case of the example of FIG.

The transversely uniaxially oriented reticulated film (transverse web) obtained above is conveyed to (4) thermocompression bonding step 317. On the other hand, the same vertical web 410 as the above is unrolled from the original roll unrolling roll, run at a predetermined feeding speed, sent to the widening step 411, widened several times by the above widening machine, and heat-treated if necessary. This vertical web was layered on the horizontal web and sent to the thermocompression bonding step 317, where the vertical web and the horizontal web were laminated so that the orientation axes intersected and thermocompression bonded, and a defect inspection such as skipping was performed. After that, the product is conveyed to a winding step 318 to obtain a product of a weft-woven laminated nonwoven fabric.

The third invention of the present application is the thermoplastic resin layer (I).
Of at least one surface of the resin layer (I) uniaxially oriented body formed by laminating the following adhesive layer (II) having a melting point lower than that of the thermoplastic resin, or uniaxially oriented body mutually through the adhesive layer (II) It is a reinforced laminate containing a substrate and at least one kind of orientation material selected from a laminate formed by laminating a plurality of sheets, a non-woven fabric and a woven fabric.

The substrate used in the present invention includes paper, synthetic resin film or sheet, foamed film or sheet, rubber sheet, porous film, random nonwoven fabric,
It is at least one selected from woven fabrics, metal foils, and the like.

Examples of the paper include kraft paper, Japanese paper, glassine paper, paperboard and the like, which may be printed.

Examples of the synthetic resin film or synthetic resin sheet include polyolefin such as polyethylene and polypropylene, polystyrene, polyester, polyamide, ethylene-vinyl acetate copolymer saponified product, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polycarbonate, A film or sheet molded from acrylic resin or the like can be used. Among these, polyolefin
In particular, a polypropylene film or sheet is most versatile and suitable in terms of economy, heat resistance, mechanical strength and the like. These films or sheets may be directly attached to a non-woven fabric or the like by the T-die method or the like, and the laminating method is not particularly limited.

As the foam film or foam sheet,
Although not particularly limited, generally polyethylene,
Examples include those using a thermoplastic resin such as polyolefin such as polypropylene, polystyrene, polyester and polyamide. Of these, a foamed film or a foamed sheet made of polyolefin, particularly polypropylene, is preferable from the viewpoint of economical efficiency, heat resistance, mechanical strength and the like.

As the rubber sheet, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, acrylonitrile-styrene copolymer rubber, SIS (styrene-
Examples thereof include isoprene-styrene block copolymer), SBS (styrene-butadiene-styrene block copolymer), polyurethane, and the like, which may be directly bonded to a non-woven fabric by a T-die method, etc. Is not particularly limited.

The porous film is produced from polyolefin such as polyethylene and polypropylene, polystyrene, polyester, polyamide, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polycarbonate, etc., and particularly polypropylene. A porous film is preferable in terms of economy, heat resistance, mechanical strength and the like. The production of the porous film can be appropriately carried out by, for example, a method of blending the above resin with a filler or the like and stretching after film formation, a method of extracting the film with a solvent, or the like, and is not particularly limited.

The random non-woven fabric includes those obtained by accumulating multifilaments, staple fibers and the like. More preferably, it is a fibrous random nonwoven fabric using a high melting point first fiber and a low melting point second fiber. Specific examples of the fibrous random nonwoven fabric are as follows. (1) Random nonwoven fabric obtained by accumulating a mixture of a high melting point first fiber or its film and a low melting point second fiber or its film or a heat-adhesive resin, (2) forming a core component Random nonwoven fabric obtained by accumulating composite fibers composed of a high melting point first fiber and a low melting point second fiber forming a sheath component, (3) a high melting point first fiber and a low melting point A random non-woven fabric obtained by accumulating side-by-side composite fibers composed of two fibers, (4) a random non-woven fabric obtained by accumulating meltblown filaments, (5) high melting point synthetic pulp and / or fibers or a web thereof, Random non-woven fabrics and the like obtained by making paper with low melting point synthetic pulp and / or fibers or a web thereof are included.

Examples of the high melting point first fibers include high density polyethylene, polypropylene, polyester, polyamide, synthetic fibers such as acrylic resin, and natural fibers such as cotton, wool and hemp. If necessary, rock wool,
Mineral fibers such as metal fibers, glass fibers and whiskers may be used in combination.

Specific examples of the core-type or side-by-side type composite fibers include high-density polyethylene (HDPE) / low-density polyethylene (LDPE), HDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / polyvinyl alcohol. (PVA), polypropylene (PP) / propylene-ethylene copolymer (PEC), PP / HDPE, P
Examples include various combinations of P / PVA, polyester (PEs) / copolyester (CPEs), PEs / HDPE, PEs / PP, polyamide (PA) / PP, PA / HDPE and the like. Products include "NBF" (trademark, manufactured by Daiwa Spinning Co., Ltd.), "ES fiber" (trademark, Chisso)
Co., Ltd., "UC fiber" (trademark, Ube Nitto Kasei)
Ltd.), "Elves" (trademark, Unitika Ltd.),
"Sunmore" (trademark, manufactured by Sanwa Paper Co., Ltd.) and the like can be mentioned.

The non-woven fabric made of the melt blow filament is made of thermoplastic resin such as polyolefin, polystyrene, polyester, polyamide, ethylene-vinyl acetate copolymer saponified product, polyvinyl chloride, polyvinylidene chloride, polycarbonate, etc. The melt blown nonwoven fabric to be manufactured is mentioned. Among these, polyolefins, especially those using polypropylene are preferable in terms of economical efficiency, heat resistance, mechanical strength and the like.

The woven fabric used as the substrate includes woven fabrics of organic and inorganic fibers such as flat yarns and multifilaments of synthetic resin, natural fibers, synthetic fibers, glass fibers and carbon fibers, and is not particularly limited. Not a thing.

Further, as the metal foil used as the base material,
Examples include foils of aluminum, iron, nickel, gold, silver and the like. Among these, aluminum foil is particularly preferable in terms of economical efficiency and mechanical strength.

As the method for producing the reinforced laminate in the present invention, extrusion lamination method, dry lamination method, or heat-bonding after the substrate and / or the non-woven fabric or the woven fabric is subjected to physical surface treatment such as corona discharge treatment. And the like. As another method, the uniaxially oriented body of the present invention, a non-woven fabric or a woven fabric is used as a support, and a random non-woven fabric or the like composed of the core type or parallel type composite fibers is directly melt-blended on the support to be integrated with the support. May be.

An example of the reinforced laminate of the present invention is S /
F, F / S '/ F, S' / Al, A / K, A / MP, A / HS,
A / MF etc. are mentioned. The above symbols represent the following. S: Two-layer uniaxially oriented film consisting of high-density polyethylene (HDPE) / adhesive layer S ': Three-layer uniaxially oriented film of adhesive layer / HDPE / adhesive layer F: High-pressure radical method low-density polyethylene (LDPE)
Film Al: Aluminum foil A: Nonwoven fabric consisting of a three-layer uniaxially oriented film of adhesive layer / HDPE / adhesive layer K: Kraft paper MP: Porous film HS: Foamed sheet MF: Meltblown nonwoven fabric

The reinforced laminate of the present invention is used for leisure sheets, automobile hoods, agricultural covering materials, cement bags, asphalt bags, synthetic resin pellet bags, adhesive tape substrates, masking films, etc. Woven fabrics are agricultural covering materials, golf course green covers, filters, drainage bags, various bags, oil adsorbents, flower wraps, house wraps, mats, wipers, waste materials such as agricultural and horticultural materials, construction materials, Used for household items.

[0107]

BEST MODE FOR CARRYING OUT THE INVENTION A uniaxially oriented body is formed by laminating an adhesive layer (II) made of a specific composition having a melting point lower than that of a thermoplastic resin on at least one surface of the thermoplastic resin layer (I), The uniaxially oriented body is laminated on each other via an adhesive layer (II) to form a laminated body, and a non-woven fabric or a woven fabric is formed by laminating the above specific uniaxially oriented body, and further laminated with a base material. By using the reinforced laminate, various materials having excellent tear resistance, adhesive strength and the like can be easily and rapidly produced.

[0108]

EXAMPLES The present invention will be described in more detail below with reference to examples. The test method used is as follows. (1) Melt flow rate It was measured based on ASTM D1238-57T (190 ° C, 2.16 kg load). (2) Density Measured according to ASTM D1505-68. (3) Measurement by DSC A sheet with a thickness of 0.2 mm is formed by hot pressing to obtain about 5 mg.
After punching out the sample of 2 and holding it at 230 ℃ for 10 minutes, 2
Cool to 0 ° C. at a rate of ° C./min, raise again to 170 ° C. at a rate of 10 ° C./min, and set the temperature corresponding to the apex of the maximum peak appearing during that period as the maximum melting point (Tm). (4) Molecular weight distribution (Mw / Mn) Using a GPC device manufactured by Waters, using o as a solvent
-Measurement was carried out with dichlorobenzene at a temperature of 135 ° C. (5) Adhesive strength of vertical and horizontal fibers Using Utensil (trade name, manufactured by Toyo Sokki Co., Ltd.), a U-shaped device connected to a load cell of Tensilon from the upper part to the center of the test piece (200 mm long × 150 mm wide) Hang on
Fix the bottom of the test piece to Tensilon. Tensile speed 500
Pull at mm / min and chart speed of 50 mm / min, and find the average value of the change in load instruction value (kg) when the mesh of the test piece is broken. (6) Low-temperature heat-sealing property A heat-sealing tester is used to perform heat-sealing with a sealing width of 5 mm, a sealing time of 1 second and a sealing pressure of 2 kg / cm ² . Using a Tensilon, a 180 mm peel test is performed on a 25 mm wide test piece at a tensile speed of 300 mm / min to determine the minimum temperature at which the peel strength is 150 g / 25 mm width or more. (7) Tensile Strength and Elongation Using a low-speed tension type tensile tester (shopper type), setting the gap between the upper and lower parts of the grips of the tester to 100 mm, the test piece (length 200 mm x width 50 mm) Fix both ends and pull at a pulling speed of 200 mm / min to determine the load (kg / 5 cm width) and elongation (%) when the test piece is cut. (8) Adhesive strength of reinforced laminated body A test piece (length 100 mm x width 20 mm) was cut out from the laminated body, one end of the test piece was peeled off by hand by about 30 mm in advance, and the end of the test piece was placed above and below the tensilon. It is attached to the grip of No. 1 and pulled at a pulling speed of 300 mm / min to measure the 180 ° peel strength of the test piece.

<Polymerization of Ethylene / α-Olefin Copolymer (A)> (Preparation of Solid Catalyst) Purified toluene was placed in a catalyst preparation device (1) equipped with an electromagnetic induction stirrer under nitrogen, and then dipropoxydichlorozirconium (Zr (OC ₃ H ₇ ) ₂ Cl ₂ ) 28
g and 48 g of methylcyclopentadiene were added,
While maintaining the system, 45 g of tridecylaluminum was added dropwise, and after completion of the addition, the reaction system was maintained at 50 ° C. and stirred for 16 hours. This solution is designated as solution A. Next, under a nitrogen atmosphere, another purified catalyst preparation device (2) with a stirrer was charged with purified toluene, and the solution A was added thereto, and then methylaluminoxane 6.4 m.
A toluene solution of ol was added and reacted. This is designated as solution B. Next, put purified toluene into a preparer (1) equipped with a stirrer under nitrogen, and then add 1400 g of silica (grade # 952, surface area 300 m ² / g; manufactured by Fuji Devison Chemical Co., Ltd.) that was previously calcined at 400 ° C. After that, the whole amount of the solution B was added, and the mixture was stirred at room temperature. Then, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This is designated as catalyst C.

(Polymerization of Sample A1) Ethylene and 4-methyl-pentene-1 were copolymerized at a polymerization temperature of 70 ° C. and a total pressure of 20 kgf / cm ² G using a continuous fluidized bed gas phase polymerization apparatus. . The gas composition in the system was 4-methyl-pentene-1 / ethylene molar ratio of 0.12 and ethylene concentration of 60 mol%. The catalyst C was continuously supplied to carry out polymerization, and each gas was continuously supplied to keep the gas composition in the system constant. The physical properties of the produced copolymer were as follows. The relationship between d and log [MFR] satisfies the condition (f). MFR: 1.5 g / 10 min Density (d): 0.918 g / cm ³ Maximum melting point (Tm): 118 ° C. Molecular weight distribution (Mw / Mn): 2.4 Cb: 1.34 ODCB soluble content (X) : 1.8wt% Value on the right side of the formula [II]: 3.8wt% Peak number of TREF curve: Multiple

(Polymerization of Sample A2) Polymerization was carried out in the same manner as in Sample A1 except that 1-butene was used as the comonomer. The physical properties of the copolymer were as follows. d and
The relationship with log [MFR] satisfies the condition (f). MFR: 1.4 g / 10 min Density (d): 0.911 g / cm ³ Maximum melting point (Tm): 115 ° C Molecular weight distribution (Mw / Mn): 2.3 Cb: 1.16 ODCB soluble content (X) : 2.7 wt% Value on the right side of the formula [II]: 6.0 wt% Peak number of TREF curve: Multiple

(Polymerization of Sample A3) Polymerization was carried out in the same manner as in Sample A1 except that 1-hexene was used as the comonomer. The physical properties of the copolymer were as follows. d
And the relationship between log [MFR] satisfy the condition (f). MFR: 1.4 g / 10 min Density (d): 0.920 g / cm ³ Maximum melting point (Tm): 119 ° C Molecular weight distribution (Mw / Mn): 2.6 Cb: 1.38 ODCB soluble component (X) : 1.6 wt% Value on the right side of the formula [II]: 3.2 wt% Peak number of TREF curve: Multiple

The olefin polymer (IIB) used is as follows. (B1) Ethylene / butene-1 copolymer (trade name: Nisseki Linirex BF3310, manufactured by Nippon Petrochemical Co., Ltd.) MFR (g / 10 minutes): 2.0 Density (g / cm ³ ): 0.925 Melting point (° C): 122 (one peak) (B2) Ultra-low density polyethylene (trade name: Nisseki Softlex D9510, manufactured by Nippon Petrochemical Co., Ltd.) MFR (g / 10 minutes): 1.0 Density (g / cm ³ ): 0.905 Melting point (° C): 121 (1 peak) (B3) High-pressure radical polymerization low density polyethylene (trade name: Nisseki Lexlon F30EE, Nippon Petrochemical Co., Ltd.)
MFR (g / 10 minutes): 3.0 Density (g / cm ³ ): 0.924 (B4) ethylene-vinyl acetate copolymer (trade name: Nisseki Lexron V270, manufactured by Nippon Petrochemical Co., Ltd.) ) MFR (g / 10 minutes): 1.5 Vinyl acetate content (% by weight): 15 (B5) ethylene-ethyl acrylate copolymer (trade name: Nisseki Lexlon EEAA2100, Nippon Petrochemical Co., Ltd.
MFR (g / 10 minutes): 1.5 Ethyl acrylate content (wt%): 10

<Experimental Examples 1 to 14> (Production of Nonwoven Fabric) In the film forming process shown in FIG. 9, high density polyethylene (density = 0.956 g / cm ³ , MFR = 1.0 g) was used.
/ 10 minutes, trade name: Nisseki Staflen E710, manufactured by Nippon Petrochemical Co., Ltd., hereinafter referred to as “HDPE”) as a core layer and adhesive layers on both sides thereof (co) polymers shown in Tables 1 and 2 Alternatively, by arranging the composition, a multilayer film having a width of 1 m and having a three-layer structure having an adhesive layer of 25 μm / core layer of 100 μm / adhesive layer of 25 μm was produced by a multilayer water-cooled inflation method. Next, in the orientation step, the multi-layer film was run and oriented up to an orientation magnification of 8. Next, in the splitting step, the film is brought into contact while rotating the splitting tool disclosed in Japanese Utility Model Publication No. 51-38979, and a zigzag split treatment is applied in the longitudinal direction to obtain a longitudinal uniaxially oriented reticulated film (a). It was made. Next, in the widening step, the longitudinal uniaxially oriented reticulated film is widened 2.5 times in the lateral direction, and in the laminating step, the widened vertically uniaxially oriented reticulated film is laminated back and forth so that the orientation axes cross each other, and the adhesion temperature The nonwoven fabric (A) was produced by heat fusion at 120 ° C. The results of measuring the adhesive strength of the longitudinal and transverse fibers and the low temperature heat sealability are shown in Tables 1 and 2.

[0115]

[Table 1]

[0116]

[Table 2]

(Evaluation of Experimental Examples) As shown in Tables 1 and 2 above, Experimental Examples 1 to 3 using an adhesive comprising the specific ethylene / α-olefin copolymer or the composition thereof according to the present invention. , 8, 9, 11, 12 and 14 have good adhesiveness and low temperature heat sealability. On the other hand, the nonwoven fabric of Experimental Example 4 using the adhesive layer having a composition outside the scope of the present invention has a high heat sealing temperature and low adhesiveness, and the nonwoven fabrics of Experimental Examples 5 to 7, 10 and 13 are It can be seen that the heat seal temperature is not so high, but the adhesiveness is low.

<Experimental Example 15> Used in the above Experimental Example 1 (A
1) A longitudinally uniaxially oriented reticulated film (a) consisting of a three-layer film having a layered structure of / HDPE / (A1) and a lateral uniaxially oriented reticulated film (b) having the same layered constitution as the latitudinal and latitudinal process according to the method of FIG. Then, a non-woven fabric (B) was obtained. Its tensile strength is 25kg / 5cm width, elongation is 15% and adhesive strength is 6kg.
And all were good results.

<Experimental Example 16> In the film forming process shown in FIG. 9, a composition in which 1% of pigment masterbatch (green pigment concentration 60%) was added to HDPE was used as a core layer, and an adhesive layer was formed on both sides of the composition. A copolymer (A1) is arranged in the same manner as in 1, and a multilayer water-cooled inflation method is used to produce a multilayer film having a width of 1 m, which is composed of a three-layer structure having an adhesive layer of 25 μm // core layer of 100 μm / adhesive layer of 25 μm, At that time, the contamination degree of the die lip was observed. Next, in the alignment step, the multilayer film was run and oriented up to an orientation magnification of 8. Next, in the split process,
No. 38979, the length of a split 20, which is split in a zigzag pattern in the longitudinal direction by abutting the film at a running speed of 80 m / min while rotating the fiber splitting tool.
A vertical uniaxially oriented reticulated film having a length of 00 m was produced, and the splitting property was observed during that period. As a result, the die is cleaned 3 to 4 times /
250 hours, no cracks or skips when splitting
It was about 1 piece / 5000 m. In addition, "interlaced" means that the branch fiber of the longitudinal uniaxially oriented reticulated film has a branching of 5 cm or less, and "small crack" means that the branch fiber has a branching of more than 5 cm and 10 cm or less. If there is more branching, it is called a "large crack".

<Experimental Example 17> The result of observing the splitting property in the same manner as in Experimental Example 16 except that the pigment masterbatch (green pigment concentration 60%) was added to the adhesive layer made of the copolymer (A1). It was necessary to clean the die once every eight hours, and there were numerous small cracks or skips on the entire surface during splitting, and large cracks were also found, making it impossible to produce a product.

<Experimental Examples 18 and 19> In Experimental Example 16 above, 1,000 ppm of a hindered amine weathering agent was added instead of the pigment masterbatch, and the effect of the weathering agent was applied to the longitudinally uniaxially oriented reticulated film obtained. Carbon arc lamp type weather resistance test (JIS B7753
-1977). The results are shown in Table 3 as Experimental Example 18. In Experimental Example 19, weather resistance was evaluated without addition, and the results are shown in Table 3.

[0122]

[Table 3]

As is clear from the table, in the case of Experimental Example 18 in which 1,000 ppm of the weatherproofing agent was added to the HDPE of the core layer, the residual ratio of various strengths and elongations was 50% or more even after 1800 hours had elapsed. However, in the case of Experimental Example 19 in which no additive is added, the amount is remarkably decreased after 900 hours.

<Experimental Examples 20 to 25> In the same manner as in Experimental Examples 1 to 14, non-woven fabric (A) was produced using a three-layer film in which adhesive layers having the compositions shown in Table 4 were arranged on both sides of the HDPE layer,
These nonwoven fabrics and various substrates are heated to a cylinder temperature of 12
A reinforced laminate was obtained by laminating and adhering at 0 ° C. The results of measuring the adhesive strength of the laminate are shown in Table 4. It can be seen that Experimental Examples 20, 23 and 24 using the adhesive layer according to the present invention show excellent adhesive strength.

[0125]

[Table 4]

[0126]

INDUSTRIAL APPLICABILITY The uniaxially oriented body of the present invention has a specific ethylene / α-olefin copolymer as an adhesive layer (II) when a multilayer film is formed based on a thermoplastic resin layer (I) having a high melting point. It has excellent adhesive strength and low-temperature heat-sealing property, and also has good mechanical strength such as tear strength, and the laminate, non-woven fabric and woven fabric formed by using it also have excellent properties. Have. In particular, non-woven fabrics and woven fabrics have a high adhesive strength of the longitudinal and transverse fibers constituting them, and do not cause any troubles in each process such as film formation, splitting, laminated thermocompression bonding during production, and the products are low-temperature heat-sealed. Since it is excellent in properties and the like, it is possible to increase the speed in bag making and in manufacturing a reinforced laminate. Also,
By adding additives such as a light-proofing agent and a colorant to the thermoplastic resin layer (I) of the inner layer such as a non-woven fabric, the moldability at the time of film formation is improved, and the defective splitting portion at the time of splitting after orientation is formed. Occurrence can be prevented. Furthermore, it is possible to improve the adhesive strength of the reinforced laminate comprising another substrate and a uniaxially oriented body, a non-woven fabric or a woven fabric.

[Brief description of drawings]

FIG. 1 is a graph showing an example of elution temperature-IR absorption curve by TREF.

FIG. 2 is a graph showing another example of elution temperature-IR absorption curve by TREF.

FIG. 3A is a partially enlarged perspective view of an example of a vertically uniaxially oriented reticulated film.

FIG. 4B is a partially enlarged perspective view of an example of a laterally uniaxially oriented reticulated film.

FIG. 5 (c) is a partially enlarged perspective view of an example of a uniaxially oriented multilayer tape.

FIG. 6 is a partial plan view of a nonwoven fabric (A) (a / a).

FIG. 7 is a partial plan view of a non-woven fabric (C) (c / c).

FIG. 8 is a partial perspective view of the woven fabric (D).

FIG. 9 (a) is a schematic view of an example of a manufacturing process of a longitudinal uniaxially oriented network film.

FIG. 10 is a schematic view of an example of a manufacturing process of a nonwoven fabric (A).

FIG. 11 is a schematic view of an example of a manufacturing process of a nonwoven fabric (B).

[Explanation of symbols]

 1 (a) Longitudinal uniaxially oriented network film 2 Thermoplastic resin layer (I) 3 Adhesive layer (II) 4 Stem fiber 5 Branch fiber 6 (b) Horizontal uniaxially oriented network film 7 (c) Uniaxially oriented multilayer tape 11, 311 Main Extruder 12, 312 Sub-extruder 13, 313 Multi-layer annular die 14, 314 Water-cooled inflation 15 Oven 16 Splitter 17 Heat treatment 18, 114, 318 Scraping 110, 410 Vertical web 111, 211, 411 Widening 112 Lamination 113 Thermocompression 210 Horizontal Web 315 Transverse slit 316 Transverse orientation 317 Laminated thermocompression bonded A Non-woven fabric having a laminated structure of A (a / a) C Non-woven fabric having a laminated structure of C (c / c) D (c) Woven fabric

Claims (10)

[Claims] 1. A uniaxially oriented body formed by laminating an adhesive layer (II) having a melting point lower than that of the thermoplastic resin of the resin layer (I) on at least one surface of the thermoplastic resin layer (I), or A laminated body in which a plurality of uniaxially oriented bodies are laminated on each other via the adhesive layer (II), [Adhesive layer (II)] (1) Ethylene / α-olefin copolymer (A) having the following properties 100 to 20% by weight (a) Density (d) 0.86 to 0.94 g / cm ³ (b) Melt flow rate (MFR) 0.01 to 100 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1. 8 to 3.5 (d) Composition distribution parameter (Cb) 1.10 to 2.00 (2) A composition containing 80% by weight or less of another olefin polymer (B). 2. The ethylene / α-olefin copolymer (A) is a mixture of o-dichlorobenzene (OD) at 25 ° C.
The CB) soluble content (X, wt%) and d and MFR have a relationship represented by the following formula [I] or [II]. The laminated body according to. [Equation 1] 3. The ethylene / α-olefin copolymer (A) has a plurality of peaks in an elution temperature-elution amount curve by a continuous temperature rising elution fractionation method (TREF). The laminate according to claim 2. 4. The laminate according to any one of claims 1 to 3, wherein the olefin polymer (B) is at least one selected from the following ethylene polymers. Polymer] (1) Density 0.86 polymerized using Ziegler type catalyst
To 0.95 g / cm ³ of ethylene / α-olefin copolymer (B ₁ ) (2) Low-density polyethylene by high-pressure radical polymerization, ethylene / vinyl ester copolymer, or ethylene and α, β-unsaturated carboxylic acid Alternatively, a copolymer (B ₂ ) with a derivative thereof. 5. The orientation magnification of the uniaxially oriented body is 1.1 to 1
The laminated body according to any one of claims 1 to 4, which is 5. 6. The uniaxially oriented thermoplastic resin layer (I)
Is 20 to 100 μm, and the adhesive layer (II) has a thickness of 3 to 60 μm. 7. A longitudinally uniaxially oriented reticulated film formed by laminating an adhesive layer (II) having a melting point lower than that of the thermoplastic resin of the resin layer (I) on at least one surface of the thermoplastic resin layer (I). At least one selected from (a), a lateral uniaxially oriented network film (b) and a uniaxially oriented multilayer tape (c).
Kind of uniaxially oriented body, or a non-woven fabric or woven fabric obtained by laminating a plurality of the uniaxially oriented bodies with the adhesive layer (II) interposed therebetween, [adhesive layer (II)] (1) ethylene having the following properties -Α-olefin copolymer (A) 100 to 20% by weight (a) Density (d) 0.86 to 0.94 g / cm ³ (b) Melt flow rate (MFR) 0.01 to 100 g / 10 min ) Molecular weight distribution (Mw / Mn) 1.8 to 3.5 (d) Composition distribution parameter (Cb) 1.10 to 2.00 (2) Composition containing 80% by weight or less of other olefin polymer (B) Stuff. 8. An adhesive layer (II) comprising at least one uniaxially oriented body selected from the longitudinal uniaxially oriented reticulated film (a), the lateral uniaxially oriented reticulated film (b) and the uniaxially oriented multilayer tape (c). The non-woven fabric or woven fabric according to claim 7, wherein the non-woven fabric or woven fabric is laminated or woven so that the orientation axes intersect with each other. 9. The uniaxially oriented thermoplastic resin layer (I)
The uniaxially oriented body, the laminate, the nonwoven fabric or the woven fabric according to any one of claims 1 to 8, characterized in that at least one additive selected from a filler, a pigment and a weather resistance agent is blended therein. 10. A uniaxially oriented body formed by laminating an adhesive layer (II) having a melting point lower than that of the thermoplastic resin of the resin layer (I) on at least one surface of the thermoplastic resin layer (I),
Alternatively, a laminated body formed by laminating a plurality of the uniaxially oriented bodies with each other with the adhesive layer (II) interposed therebetween, a reinforced laminated body containing at least one orienting material selected from a non-woven fabric and a woven fabric, and a base material, [Adhesive Layer (II)] (1) 100 to 20% by weight of ethylene / α-olefin copolymer (A) having the following properties (a) Density (d) 0.86 to 0.94 g / cm ³ (b) ) Melt flow rate (MFR) 0.01 to 100 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.8 to 3.5 (d) Composition distribution parameter (Cb) 1.10 to 2.00 (2) A composition containing 80% by weight or less of another olefin polymer (B).