JPH04130151A - Vinyl chloride resin composition, film or sheet made therefrom, and container and packaging material - Google Patents

Abstract

PURPOSE:To enable the printing with a UV curable ink and improve transparency, coatability, etc., by compounding a vinyl chloride resin with a vinyl ester (co)polymer having specific linking units in the side chains. CONSTITUTION:A vinyl chloride resin, 0.1-30wt.% vinyl ester (co)polymer which pref. comprises an ethylene-vinyl ester copolymer contg. 50wt.% or higher vinyl ester units and contains linking units of the formula (wherein (x) is 3 or 4; (y) is 1 or 2; and M is metal) introduced into the side chains by radical polymn. in an amt. of 600-200000 in terms of SO3M or SO4M group equivalent, and, if necessary, a pigment, a stabilizer, a lubricant, a plasticizer, a flame retardant, etc., are compounded to give the title compsn., which is formed into a film, a sheet, a laminate, etc., to be used for a container, a packaging material, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a vinyl chloride resin composition with improved printability and paintability, a film or sheet, and a container/packaging material using the same.

[Prior Art] Conventionally, vinyl chloride resins have been widely used for various purposes because they have excellent mechanical properties, are inexpensive, and are easy to mold. These sheets and films are widely used as packaging materials, mainly in the food industry, and colorful products are provided using gravure printing and screen printing. Ink using organic solvents such as toluene and ethyl acetate is used for printing. These organic solvents have a good affinity with the vinyl chloride film that is the printing base material, and cannot be sufficiently removed in the drying process. As a result, organic solvents migrate into the packaged items, such as foods, and this poses a sanitary problem. In order to improve this problem and speed up the drying process after printing, attempts are being made to use ultraviolet curable inks that do not contain organic solvents. However, since UV-curable inks do not contain organic solvents, they have caused a new problem of poor adhesion to vinyl chloride films.

[Problems to be Solved by the Invention] An object of the present invention is to provide a vinyl chloride resin composition that can be printed even with an ultraviolet curable ink that does not contain an organic solvent and has excellent transparency.

[Means for Solving the Problems] In view of the above circumstances, the present inventors have conducted extensive research in order to obtain a vinyl chloride resin that can be printed with ultraviolet curable ink and has excellent transparency. −←SOx)yM (
x=3. 4;y=1. 2; M is a metal) It has been found that by blending a vinyl ester polymer or copolymer having a bonding unit in the side chain, the adhesion between the vinyl chloride resin and the ink is improved and transparency is also excellent.
This led to the present invention.

That is, the present invention is based on →S Ox)yM (x= 3.4
; y=1.2; M is a metal) vinyl ester polymer or copolymer having a bonding unit in the side chain, preferably →SOx)yM (x=3.4; y=1.
2; M is a metal) is an ethylene-vinyl ester copolymer into which a bonding unit is introduced by radical polymerization, especially an ethylene-vinyl ester copolymer having a vinyl ester content of 50% by weight or more.
The present invention provides a vinyl chloride resin composition containing a vinyl ester copolymer with improved printability, a film or sheet, and a container/packaging material using the same.

[Constitution] The vinyl chloride resin used in the present invention includes a vinyl chloride homopolymer, a monomer copolymerizable with vinyl chloride,
For example, vinyl esters such as vinyl acetate; olefins such as ethylene; acrylic acid, methacrylic acid and their alkyl esters; copolymers with vinyl chloride containing up to 30% by weight of vinylidene chloride, and furthermore ethylene. Vinyl acetate copolymers, chlorinated polyethylene, and graft copolymers obtained by adding vinyl chloride to thermoplastic polyurethane can also be used.

The vinyl ester polymer or copolymer used in the present invention may be one that is compatible with the vinyl chloride resin. For example, vinyl acetate homopolymer or vinyl formate homopolymer, ethylene-vinyl ester copolymer (vinyl esters include, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl laurate, vinyl benzoate), or their saponification. There are things etc. Among these, ethylene-vinyl ester copolymer is preferred.

In particular, the vinyl ester content in the ethylene-vinyl ester copolymer is preferably 50% by weight or more.

If the vinyl ester content is less than 50% by weight, the effect of improving printability will not be satisfactory, so it is not preferable.

■SOx)yM (x=3.4;
As a vinyl ester polymer or copolymer having a bonding unit (y=1,2; M is metal) in the side chain, →S
Ox)yM, preferably a metal base of sulfonic acid or sulfuric acid, →S Ox)y
A radically polymerizable monomer having a bond unit M is radically copolymerized when producing a vinyl ester polymer or copolymer, or the radically polymerizable monomer is grafted onto a vinyl ester polymer or copolymer. Examples include those introduced under polymerization conditions.

The vinyl ester polymer or copolymer having →SoX)yM bonding unit in the side chain used in the present invention is one in which the −+SOx)yM group has SO3M group or Ha804M group equivalent of 600 to 2000oO. It is preferable that

The content of the vinyl ester polymer or copolymer in the vinyl chloride resin composition is preferably 0.1 to 30% by weight, and the content of the SOx)yM group in the composition is SO, M group or 504M group equivalent, 2000~
Preferably, it is 2,000,000. If it is less than 2,000, the sheet will take on a yellowish tinge during molding of the vinyl chloride resin composition, resulting in decreased transparency, and if it exceeds 2,000,000, the effect of improving printability will be insufficient, which is not preferred.

Note that the equivalent weight of →S Ox)yM group represents the number of grams of a (co)polymer or composition containing 1 gram equivalent of SO, M group, or 804M group.

→ The content of the radically polymerizable monomer having a bonding unit of 3 o x) yM is 0
．． 01 to 10% by weight is preferred. If it is less than 0.01% by weight, the effect of improving printability will be insufficient, and if it exceeds 10% by weight, the sheet will take on a yellowish tinge and transparency will decrease during molding of the vinyl chloride resin composition, which is not preferable.

→S Ox)yM (x= 3.4
Examples of the radically polymerizable monomer having a bonding unit (y=1,2; M is metal) include sodium vinylsulfonate, sodium methacrylsulfonate, sodium styrenesulfonate, sodium sulfoalkyl methacrylate, and 2-acrylamide-2. -Sodium alkylpropanesulfonate, alkylarylsulfocoa% sodium phosphate, sodium vinyl sulfate, zinc methacrylsulfonate. Also, →S Ox)y
When introducing a radically polymerizable monomer having a bonding unit M (x = 3゜4; y-1,2; M is a metal),
If necessary, vinyl monomers other than the above radically polymerizable monomers, such as fatty acid vinyl esters such as vinyl acetate and vinyl propionate, acrylic acid or methacrylic acid such as ethyl acrylate, methyl acrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, and methyl methacrylate; Alkyl esters, aromatic vinyls such as styrene, vinyl cyanides such as acrylonitrile, etc. may be used in combination.

1+SOx)yM (x=3.4;y=1.2
; M is a metal) can be introduced into a vinyl ester polymer or copolymer using general polymerization methods such as melt grafting using an extruder or graft polymerization in a solution. For example, in the case of a polymerization method, it is carried out as follows.

That is, in the vinyl ester polymer or copolymer in suspension →S Ox)yM (x= 3.4; y= 1
゜2; M is a metal) A radically polymerizable monomer having a bonding unit is added to the vinyl ester polymer or copolymer particles to form the SOx)yM (x=3.4; y=1
, 2; M is a metal), and then polymerization is carried out using a radical initiator at elevated temperature. These radical initiators include benzoyl peroxide, azobisisobutyronitrile,
t-Butyl peroxybenzoate, t-butyl peroxy (2-ethylhexanoate), diisopropyl peroxy carbonate, t-butyl peroxy pinocrate, t-butyl peroxy isopropyl carbonate, t-butyl lauryl peroxide, etc. and these are →S Ox)yM (x= 3.4; Y=1
．． Polymerization is usually carried out by adding 0.1 to 1 part by weight to 100 parts by weight of a radically polymerizable monomer having a bonding unit of 2; M is a metal. The polymerization temperature varies depending on the radical initiator used, but is generally 60 to 130''C, and the resulting suspended state →S○x)yM (x=3.4;
y=1. A vinyl ester polymer or copolymer having a bonding unit (M is a metal) in its side chain is separated from water, washed, and dried.

An anti-blocking agent such as wax, silicone oil, silica, calcium carbonate, magnesium oxide, calcium stearate, etc. may be used at the time of application, and the amount to be added is as follows:
SOx)yM (x= 3.4; y= 1゜2
; M is metal) is preferably 0.00 parts by weight per 100 parts by weight of the vinyl ester polymer or copolymer having a bonding unit in the side chain. It is 1 to 10 parts by weight.

Other polymers may be blended within a range that does not impair the effects of the present invention. Examples of other polymers include EVAS 5BR
Examples include rubber and plastics such as SABS, chlorinated polyethylene, polyurethane, and polyester.

Furthermore, the vinyl chloride resin composition of the present invention may contain pigments, stabilizers, lubricants, plasticizers, flame retardants,
Processability improvers, antistatic agents, crosslinking agents, etc. can be added.

In order to obtain the vinyl chloride resin composition of the present invention, the vinyl chloride resin, →SOx>yM (x=3.4;
The objective can be achieved by uniformly mixing a vinyl ester polymer or copolymer having a bonding unit (y=1,2; M is a metal) in the side chain. Mixing methods include commonly used extruders, mixer rolls,
Is there a method of kneading in a molten state using a mixer such as a kneader roll mill, a Banbury mixer, or a continuous mixer? A more uniform treated product or composition can be obtained by mixing using a mixer. In addition, before carrying out these mixing operations, tri-blending is performed in advance using a mixer such as a drum tumbler or a Henschel mixer, and the resulting mixture is further melt-kneaded to obtain a more uniform treated product or composition. I can do it. Furthermore, a part of these mixed components (composition components) may be mixed in advance to produce a so-called masterbatch, and the resulting masterbatch (mixture) and the remaining mixed components may be mixed.

In order to process the vinyl chloride resin composition obtained in this way or its compound (additive) into a desired shape, such as a molded article, film, sheet, multilayer laminate, etc., extrusion molding method, injection molding method, etc. This can be achieved using normal processing methods such as the method and calender processing method. By such a method, containers and packaging materials with excellent printability can be obtained.

〔Example〕

Next, in order to further clarify the characteristics of the present invention, the present invention will be specifically explained using examples. In addition, the number of copies and percentages in Examples and Comparative Examples
All are on a weight basis. Further, processing methods, printing methods, and evaluation methods of the compositions used in Examples and Comparative Examples are as follows.

(1) Processing method of composition 100 parts of vinyl chloride resin with a degree of polymerization of 800, 15 parts of dioctyl phthalate, 8 parts of MBS resin (Kane Ace B-12 manufactured by Kanebuchi Kagaku Co., Ltd.), 1.5 parts of octyltin mercapto, glycerin monostear rate 1 part and -(SOx)y
5 parts of a vinyl ester polymer or copolymer having a bonding unit of
．． A 3 mm thick sheet was prepared and evaluated for printability and transparency.

(2) Transparency evaluation method The transparency evaluation of the vinyl chloride resin composition is determined by (1)
The total light transmittance of the sheet obtained in ) was measured, and a sheet of 80% or more was rated as good transparency.

Less than 80% was marked as x.

(3) Sheet printing method Apply ultraviolet curable ink (Dainippon Ink Chemicals, Daikinia OL Ai) to the sheet surface obtained in (1) using an RI tester (2-split roll, 0.15cc). Develop the color and irradiate it with ultraviolet rays under UV clamp 0W/cm 1
0 m/min (1 pass)) to obtain a printability evaluation test sheet.

(4) Printability evaluation method (adhesion) A test was conducted using a cellophane tape peel test. A commercially available cellophane tape was applied and then peeled off. ○: If there is no ink transfer to the cellophane tape at all, if the ink is transferred to the cellophane tape on a part of the adhesion surface and some ink remains on the sheet, or if the ink is transferred to the entire cellophane tape on the adhesion surface. The case was marked as ×.

Example 1 In a magnetically stirred autoclave with an internal volume of 2 L, 5 parts of vinyl acetate, 800 parts of distilled water, 1.6 parts of azobisisobutyronitrile (polymerization catalyst), and 1.6 parts of polyvinyl alcohol (dispersant) were placed. 1 part and 068 parts of sodium polyacrylate (dispersant), then the air in the autoclave was replaced with nitrogen, and ethylene was added at 55 kg/cm at 30°C.
After press-fitting to 2, the internal temperature was raised to 65°C and suspension polymerization was carried out for 9 hours. After releasing the residual ethylene and returning the temperature to room temperature and normal pressure, ethylene with a vinyl acetate content of 63% was found.
A vinyl acetate copolymer (1) (hereinafter abbreviated as EVA (1)) suspension was produced. To 840 parts of this EVA (1) suspension (resin content 25%), 0.7 parts of polyvinyl alcohol (dispersant), 75 parts of methyl methacrylate (MMA), 1 part of sodium sulfoethyl methacrylate (NaSEM)
5 parts of benzoyl peroxide (polymerization catalyst) were added thereto, and stirring was continued for 2 hours at room temperature to absorb the monomer and initiator into the suspended particles. After that, the temperature was raised to 75°C and
Time polymerization was performed. After washing the resulting particles,
Modified EVA (A) 29 by drying at 50°C for 24 hours
Got 2 copies. This modified EVA (A) is
A vinyl chloride resin composition was evaluated as a vinyl ester polymer or copolymer having a bonding unit (x=3.4; y=1.2; M is metal) in the side chain.

Example 2 Methyl methacrylate 8 parts instead of 75 parts methyl methacrylate and 15 parts sodium sulfoethyl methacrylate
1 part and sodium methacrylsulfonate (MSNa)
Modified EVA was prepared in the same manner as in Example 1 except that 9 parts were used.
(B) 289 parts were obtained.

This modified EVA (B) is −+SOx)yM (x=3
．． A vinyl chloride resin composition was evaluated as a vinyl ester polymer or copolymer having a bonding unit (4; y=1,2; M is metal) in the side chain.

Example 3 150 parts of vinyl acetate, 800 parts of distilled water, 1.6 parts of azobisisobutyronitrile (polymerization catalyst), 1.6 parts of polyvinyl alcohol (dispersant) and Add 0.8 parts of sodium polyacrylate (dispersant), then replace the air in the autoclave with nitrogen, and add 62 kg/c of ethylene at 30°C.
m", the internal temperature was raised to 65°C, and suspension polymerization was carried out for 9 hours. Residual ethylene was released, and the temperature was increased to room temperature.
When the pressure was returned to normal, an ethylene-vinyl acetate copolymer (2) (hereinafter abbreviated as EVA (2)) suspension having a vinyl acetate content of 53% was produced. This EVA (2) suspension (
0.7 parts of polyvinyl alcohol (dispersant), 75 parts of methyl methacrylate, 15 parts of sodium sulfoethyl methacrylate, and 1.8 parts of benzoyl peroxide (polymerization catalyst) were added to 840 parts of resin content (25%), and Stirring was continued for a period of time to absorb the monomer and initiator into the suspended particles. Thereafter, the temperature was raised to 75°C and polymerization was carried out for 5 hours. After washing the obtained particles, they were dried at 50°C for 24 hours to obtain 285 parts of modified EVA (C). This modified EVA
(C) -+SOx)yM (x=3.4;y=1
．． A vinyl chloride resin composition was evaluated as a vinyl ester polymer or copolymer having a bonding unit (M is metal) in the side chain.

Example 4 960 parts of EVA (1) suspension (resin content 25%) in place of 840 parts of EVA (1) suspension (resin content 25%), 75 parts of methyl methacrylate and 15 parts of sodium sulfoethyl methacrylate, Modified EVA (D) 283 in the same manner as in Example 1 except that 45 parts of styrene (St) and 15 parts of sodium styrene sulfonate (NaSS) were used.
I got the department.

This modified EVA (D) is →SOx)yM (x=
A vinyl chloride resin composition was evaluated as a vinyl ester polymer or copolymer having a bonding unit (a, 4; y=1,2; M is a metal) in the side chain.

The above results are shown in Table-1.

Comparative Example 1 75 parts of methyl methacrylate, 90 parts of methyl methacrylate instead of 15 parts of sodium sulfoethyl methacrylate
The same method as in Example 1 was used except that the modified EVA
(E) 293 parts were obtained. This modified EVA (E) →
SOx)yM (x=3.4; y=1.2;
A vinyl chloride resin composition was evaluated as a vinyl ester polymer or copolymer having a bonding unit (M is a metal) in the side chain.

Comparative Example 2 EVA (1) of Example 1 was converted to −+S Ox)yM (x=
A vinyl chloride resin composition was evaluated as a vinyl ester polymer or copolymer having a bonding unit (3°4; y=1,2; M is metal) in the side chain.

Comparative Example 3 Butyl acrylate 25% in a flask with an internal volume of 2 liters
0 parts, 750 parts of distilled water, azobisisobutyronitrile (
Polymerization catalyst) 1.6 parts, polyvinyl alcohol (dispersant)
1.6 parts and 0.8 parts of sodium polyacrylate (dispersant)
The internal temperature was raised to 65°C, and suspension polymerization was carried out for 4 hours. When the temperature was returned to room temperature, a polybutyl acrylate (hereinafter abbreviated as PBA) suspension was produced. This PB
840 parts of suspension A (resin content 25%), 0.7 parts of polyvinyl alcohol (dispersant), 75 parts of methyl methacrylate,
15 parts of sodium sulfoethyl methacrylate and 1.8 parts of benzoyl peroxide (polymerization catalyst) were added, and stirring was continued at room temperature for 2 hours to absorb the monomer and initiator into the suspended particles. Thereafter, the temperature was raised to 75°C and polymerization was carried out for 5 hours. After washing the resulting particles, they were incubated at 50°C for 24 hours.
After drying for hours, 281 parts of modified PBA was obtained. This modified PBA is 1+SOx)yM (x=3.4;
y=1. A vinyl chloride resin composition was evaluated as a vinyl ester polymer or copolymer having a bonding unit (M is a metal) in the side chain. However, since the sheet became uneven and a smooth sheet could not be obtained, it was impossible to evaluate the printability.

Comparative Example 4 Contents g250 parts of styrene in a 2 liter flask, i
750 parts of distilled water, azobisisobutyronitrile (polymerization catalyst) 1. 6 parts, polyvinyl alcohol (dispersant) 1.
6 parts and 0.8 parts of sodium polyacrylate (dispersant) were charged, the internal temperature was raised to 65°C, and suspension polymerization was carried out for 9 hours. When brought back to room temperature, polystyrene (hereinafter referred to as
A suspension (abbreviated as PS) was formed. This PS suspension (
0.7 parts of polyvinyl alcohol (dispersant), 75 parts of methyl methacrylate, 15 parts of sodium sulfoethyl methacrylate, and 1.8 parts of benzoyl peroxide (polymerization catalyst) were added to 840 parts (resin content 25%), and Stirring was continued for a period of time to absorb the monomer and initiator into the suspended particles. Thereafter, the temperature was raised to 75°C and polymerization was carried out for 5 hours. After washing the obtained particles, they were dried at 50° C. for 24 hours to obtain 288 parts of modified PS. This modified PS is −←S
A vinyl chloride resin composition was evaluated as a vinyl ester polymer or copolymer having a bonding unit Ox)yM (x=3°4; y=1,2; M is a metal) in the side chain. However, since the sheet became uneven and a smooth sheet could not be obtained, it was impossible to evaluate the printability.

The above results are shown in Table-2.

Table Example Na Trunk Type Composition Ethylene content (%) Le Quantity (%) E-modified polymerization Other monomer name Other monomer amount (%) SO, M compound amount SO, M compound amount (%) EVA EVA EVA EVA 70 8 O NaSEM MSNa NaSEM Na5SM
MA MMA MMA St PVC-based transparent composition Printability Q OO○ ○ ○ OO Table-2 Comparative example Na Stem Type Composition Ethylene content (%) Le Quantity (%) Modified polymer and other monomer names Other monomers (%) SO1M compound name SO,M compound amount (%) EVA EVA PBA PS NaSEM NaSEM MA MA MA PVC-based transparent composition Printability [Effects of the invention] The vinyl chloride-based resin composition obtained by the present invention has an organic It has excellent printability with solvent-free ultraviolet curable ink and is transparent, so it can be used in a wide range of applications. In particular, it is excellent as a container or packaging material when molded into molded articles, films, or sheets.

teenager Reason Man

Claims (1)

[Claims] 1.Contains a vinyl ester polymer or copolymer having a bonding unit of SOx)yM (x=3,4; y=1,2; M is metal) in the side chain. A vinyl chloride resin composition characterized by: 2. A vinyl ester polymer or copolymer having a bonding unit of -(SOx)yM(x=3,4; y=1,2; M is metal) in the side chain is -(SOx)yM(x=3 ,4;y
2. The vinyl chloride resin composition according to claim 1, wherein the vinyl chloride resin composition is an ethylene-vinyl ester copolymer into which a bonding unit of =1,2; M is a metal is introduced by radical polymerization. 3. The vinyl chloride resin composition according to claim 2, wherein the vinyl ester content of the ethylene-vinyl ester copolymer is 50% by weight or more. 4. A film or sheet comprising the vinyl chloride resin composition according to claims 1 to 3. 5. A container or packaging material comprising the vinyl chloride resin composition according to claims 1 to 3.