JPS5922670B2 - sheet laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides chlorinated poly9ethylene (CP) having specific physical properties.
The present invention relates to a sheet-like laminate characterized in that E) is laminated on at least one side of a base fabric made of various fibers.

The sheet-like laminate obtained by the present invention is not only easy to manufacture, but also has an extremely good balance of physical properties, and can be used in a wide range of fields such as containers, belts, waterproof clothing, and jets. It is.

Conventionally, this type of sheet-like laminate has been made of nylon, polyester,
Generally used is a base fabric made of various fibers with excellent mechanical properties such as ester and polyvinyl alcohol, with soft polyvinyl chloride (soft vinyl chloride) laminated on at least one side. C having specific physical properties according to the present invention
A sheet-like laminate made of PE has the advantages of soft PVC, while at the same time overcoming its drawbacks. In particular, unlike soft PVC laminates, it does not contain any low-molecular toxic volatile components such as plasticizers and monomers, so it has the advantage of being safe to use in fields related to food packaging, transportation, and transportation. has.

The sheet-like laminate according to the present invention has excellent flexibility, oil resistance, weather resistance, low-temperature properties, wear resistance, and chemical resistance, as well as good adhesion between the base fabric and CPE. It has excellent mechanical properties, high-frequency sealing properties, and heat sealing properties, so it is also suitable for secondary processing such as lamination and sewing. The CPE used in the present invention is produced by chlorinating poly-9ethylene powder in an aqueous suspension, and the degree of chlorination is 15 to 15.
6096, Vicat softening point 30-55℃, melting index (M
1) A crystal residual degree of 20 cm or more is required at 0.05 to 5 V/10 minutes.

Here, the degree of crystal persistence refers to the amount of heat absorbed at the crystal melting point of the raw material polyethylene per unit weight to the amount of raw material polyethylene per unit weight.
It is the ratio of endotherms at the crystalline melting point of CPE produced from ethylene, expressed as a percentage. Degree of chlorination is 15
If it is less than 60%, the flexibility will be poor and the high frequency seal will be insufficient, and if it exceeds 60%, it will be unsuitable because it will have poor workability and will be difficult to manufacture.

Those with a Vikatsu softening point of 30° C. or lower are unsuitable because they have a sticky feel even at room temperature and cause blocking under slight loading. Moreover, those exceeding 55°C are not preferable because they lack flexibility at low temperatures. MI is 0.05~
5, preferably 0.2 to 2. If the MI is low, the moldability becomes poor and the adhesion to the base fabric is extremely reduced, while if it becomes 5 or more, the durability becomes poor, which is not preferable. In general, the higher the crystal persistence, the better the high frequency sealing properties and heat sealing properties tend to be, so it is necessary that it be at least 20%. CPE that satisfies the above requirements can actually only be obtained by a chlorination reaction in an aqueous suspension of polyethylene, such as a solid-gas reaction of polyethylene and chlorine gas or dissolving polyethylene in an organic solvent. However, it cannot be obtained when chlorinated in a homogeneous system. In the former case, it is difficult to industrially produce a product with a Vikatsu softening point of 55°C or lower, and in the latter case, the residual rate of crystals is low and only a substantially amorphous rubber-like product is obtained. . The above CPE is mainly produced by chlorinating high-density polyethylene powder in an aqueous suspension. Since it is influenced by many factors such as the type of activator, the stirring speed, and the supply rate of Ct2 gas, it is necessary to take these factors into consideration when producing CPE.

CPE that meets these requirements has excellent heat resistance and moderate fluidity, and has excellent moldability, so it can be easily laminated with a base fabric using a normal processing machine. be able to.

In many cases, it is preferable to use small amounts of stabilizers, lubricants, fillers, etc., and in some cases, other soft molding materials may be used to change the adhesion and physical properties of the moldable base fabric. This does not preclude blending. Examples include low density polyethylene, ethylene/propylene copolymer, ethylene/vinyl acetate copolymer, polyvinyl chloride polyurethane, SBRlNBRchloroprene, and the like. Further, in special cases, a peroxide-based crosslinking agent may be used to carry out crosslinking during or after the lamination process. As for the forming method, it is also possible to press and laminate one or both sides of the base fabric at the same time as forming the CPE sheet by extrusion, calender, etc., or to form the sheet once and then melt and press the sheet and the base fabric to laminate. It is.

In most cases, the sheet forming temperature is preferably 100 to 180°C, and the pressure bonding temperature is preferably 140 to 220°C, preferably 150 to 190°C. In special cases, lamination can be achieved by dissolving CPE in an organic solvent and coating the base fabric with the solution. As the base fabric, a base fabric made of SLLM of polyester, nylon, or vinylon (polyvinyl alcohol) is preferable, but base fabrics made of cellulose fiber or acrylic fiber may also be used depending on the case. The present invention will be explained in more detail below with reference to Examples.

Various measurement methods used in Examples and Comparative Examples are as follows. The residual degree of crystals is 100 after kneading the raw polyethylene powder with a roll at 160°C and preheating it at 180°C for 3 minutes.
The thickness was 1.5 mm, which was produced by pressing at ~150 Kf/Cwl for 2 minutes and then cooling in a press at 25°C. sheet like 1
57! If the heat absorption amount (expressed as area) near the melting point was measured using a DSC (differential calorimeter) manufactured by Rigaku Denki Kogyo Co., Ltd. at a heating rate of 4°C/-, the same polyethylene was used as a raw material. It was determined by considering the degree of chlorination from a sheet made using CPE in exactly the same manner as above.
The endothermic amount (area) of an amount corresponding to 15 mf of polyethylene was measured in the same manner, and the ratio is expressed in %.

Picato softening is according to JISK-7206, MI is J
It was determined by ISK676O.

Example 1 Density 0.953f1/CCMI2 13.91
/10 minutes, average particle size 80 mesh, bulk density 0.451
Surface area (N, by BET method using gas adsorption) 1.95
A 100 t glass-lined autoclave was filled with d/f polyethylene powder 14 Kf pure water 80 t1 alkylbenzenesulfonic acid surfactant 301, and while stirring, chlorine gas was blown into the autoclave from the bottom to carry out the reaction under strong stirring.

The pressure of chlorine gas was set at 3 Kfr under a predetermined reaction temperature, and the amount of chlorine consumed in the reaction was measured over time. When the desired degree of chlorination was reached, the chlorine supply was stopped and the reaction was terminated.

An example of reaction conditions is approximately 30% at 110°C for 3 hours.
After further chlorination of about 10% in 4 hours, the supply of chlorine was stopped, and after cooling, the product was taken out from the autoclave and thoroughly washed by rinsing with a large amount of pure water. Dry at °C.

The degree of chlorination of the chlorinated polyethylene thus obtained was 40.
．． 4 (F6), the measured value of the residual rate of 1 crystal was 47%, and the Picato softening point was 48.5 ° C. The MI value was 0.21 (Table 1 Experimental plate 9).Hereinafter, the reaction temperature in the above example, A large number of samples were prepared at various times.

In this manner, laminate sheets were created for a number of CPE samples, each produced under slightly different reaction conditions. Calcium stearate 0.5 in CPElOO part
1 part dioctyltin maleate, 10 parts irganox
10 was added, and after kneading with two rolls at 150°C for 10 minutes, a sheet with a thickness of about 0.5 m was prepared using a press.

A plain weave base fabric consisting of 16 vertical and horizontal polyester 1000 denier multifilament yarns per inch was sandwiched between two of the above press sheets and heated at 180°C for 5 minutes at 5K.
A sheet-like laminate having a thickness of 1 m was produced by f/CTI compression bonding. The coloring degree of the sheet-like laminate thus obtained,
The flexibility and peel strength after welding using a conventional high-frequency welder were investigated. The degree of coloring was evaluated in 1 to 5 grades in descending order of coloring. No. 1 was virtually colorless, and the color changed from pale yellow to brown in the order of No. 12 to No. 5.

Practically acceptable values are 3 and preferably 2 or less.
Flexibility was evaluated by bending a 30 cm x 30 cm square sheet-like laminate at -5° C. and applying an external force such as screw b.

Evaluated on a 3-level scale, O = good, × = almost no flexibility.
When a b1 crack occurs in which the sheet becomes white, Δ is an intermediate situation.

The peel strength was expressed as the b-strength after the end of a 3 cm wide tanzak-shaped test piece cut parallel to (or perpendicular to) the weave direction of the base fabric was welded using a conventional method.

The peel strength is influenced by the strength of high frequency welding and the adhesion between the CPE and the base fabric.1 For example, peel strength of 120Kf/3cm or more is due to the destruction of the base fabric, and the peel strength is due to the breakage of the base fabric and the peel strength of the base fabric and CPE at the same time as high frequency welding. This indicates that the adhesion was complete. The test results are summarized in Table-1.

From the table above, when the degree of chlorination of CPE is low, the degree of coloration is good, but the flexibility and peel strength are insufficient, and when the degree of chlorination exceeds 50%, the degree of coloration decreases rapidly.
In addition, since the flexibility decreases, the degree of chlorination is 1.
It can be seen that it is preferable that the weight is 5 yen or more, preferably 20 dollars or more and 5596 or less.

On the other hand, even if the degree of chlorination is 30 to 4096, if the Picato softening point is high, the degree of coloring and flexibility will be poor, and if the degree of crystal persistence is low, the peel strength will tend to decrease.

When the crystal abundance is less than 20%, the laminate tends to become sticky, and when stacked one on top of the other and left under a small load, there is a tendency for welding (blocking). From the above, the Picato softening point and crystal residual degree of CPE suitable for the present invention were defined as 20 to 55°C and 20% or more, respectively. In addition, soft vinyl chloride is made by adding 70 parts of plasticizer dioctyl J to PVC with a polymerization degree of 1000, and ethylene/vinyl acetate copolymer has a vinyl acetate content of 20% and MI
= 1.5yA for 0 minutes, and is the result of examining laminates manufactured by the same method as in the case of CPE.

It can be seen that the products using the CPE of the present invention have superior physical properties, such as flexibility and peel strength, compared to these conventional products. Example 2 Among samples manufactured using various polyethylene powders with a density of 0.950 and MI: T5 to 20 under chlorination reaction conditions according to Example 1, a degree of chlorination of 30 to 32% was obtained.
A sheet-like laminate was produced by the same method as in Example 1 using a nylon base fabric, and its physical properties were examined.

Claims (1)

[Claims] 1 Produced by chlorination in aqueous suspension with a degree of chlorination of 15-55% and a Vicat softening point of 30-55
C., a melting index of 0.05 to 5 g/10 minutes, and a chlorinated polyethylene having a crystal residual degree of 20% or more is laminated on at least one side of a base fabric.