DE2937268C2 - Aqueous emulsion of a synthetic multicomponent resin and process for its preparation - Google Patents

Description

originate, the emulsion by emulsion polymerization of ethylene and component (C) in Presence of an aqueous emulsion produced by emulsion polymerization of ethylene and the component (B) has been obtained.

2. A process for the preparation of an aqueous emulsion containing 10 to 60 wt .-% solids, which in the Polymerization of

(A) Ibis 50% by weight ethylene,

(B) 4 to 95% by weight of a styrene monomer or a mixture of a styrene monomer and one monomers copolymerizable therewith and

(C) 4 to 95 Gsv /.- Ψο of a vinyl ester or a mixture of a vinyl ester and a monomer copolymerizable therewith have arisen,

characterized in that in a first stage ethylene and component (B) of the emulsion polymerization subject and in a second stage ethylene and component (C) in the presence of the the aqueous emulsion obtained in the first stage is subjected to emulsion polymerization.

3. The method according to claim 2, characterized in that the weight ratio of styrene monomers to the monomer copolymerizable therewith in component (B) is 1: 0 to 1: 3 and that the Weight ratio of vinyl ester to the monomer copolymerizable therewith in component (C) Is 1: 0 to 1: 3

4. The method according to claim 2, characterized in that the emulsion polymerization in the first Stage is carried out until the amount of unreacted monomer (B) in the resulting aqueous Emulsion is below about 300 ppm.

5. The method according to claim 2, characterized in that the emulsion polymerization in the first and the second stage in the presence of a radical-generating catalyst at a temperature of 0 to 100 ⁰ C and a pressure of 0.49 to 19.6 MPa (5 to 200 kg / cm ² ) is carried out.

6. Use of the aqueous emulsion according to claim I for the production of a film.

The invention relates to an aqueous emulsion of a synthetic multicomponent resin, with which one

can produce a film having superior properties and a method for producing the same. The emulsion

is made by emulsion polymerization of ethylene and styrene in a first stage and emulsion polymerization of ethylene and a vinyl ester in a second stage in the presence of those obtained in the first stage aqueous emulsion produced.

The aqueous emulsion of the present invention contains 10-60% by weight solids obtained by Polymerization of (A) 1 to 50% by weight of ethylene, (B) 4 to 95% by weight of a styrene monomer or a Mixture of a styrene monomer and a monomer copolymerizable therewith, and (C) 4 to 95 % By weight of vinyl ester or a mixture of a vinyl ester and a monomer which can be polymerized therewith. The important feature of this aqueous emulsion is that it is made by a process which comprises a first stage in which ethylene and a styrene monomer or ethylene and a mixture of one Styrene monomer and a monomer copolymerizable therewith to form an aqueous emulsion Be emulsion-polymerized, and in a second stage ethylene and a vinyl ester or ethylene and a mixture of a vinyl ester and a monomer copolymerizable therewith in the presence of the the aqueous emulsion produced in the first stage are emulsion-polymerized.

The inventive aqueous emulsion obtained by the above process forms a film with a relatively high hardness despite their relatively low MFT (abbreviation for minimum film-forming temperature or minimum film forming temperature). The film formed has good transparency. Flexibility, waterbed siändkcil. Alkali resistance and weather resistance as well as high breaking strength.

Many aqueous emulsions based on a copolymer of ethylene and a vinyl ester are known. For example, an aqueous emulsion made from a copolymer of ethylene and a vinyl ester, in particular vinyl acetate, is known which has an ethylene content of up to 40% by weight and has good pigment binding power ((A-PS 8 988/63). One made from this aqueous emulsion produced film has a good flexibility b ^r> and a high adhesive strength and Klcbefähigkeit. therefore, this emulsion is often in the form of paints. Klebcstoffen, Papierbchandlungsmitteln etc. are used. However, the film on the other hand has the disadvantage that it is soft and that its surface The film also has low tensile strength and relatively poor water resistance.

In an attempt to improve water resistance and saponification resistance, an aqueous one Emulsion from a terpolymer of ethylene / vinyl acetate / vinyl chloride proposed (JA-PS 37 989/73). the end Films made with this emulsion tend to yellow and have poor weather resistance Es was also an aqueous emulsion of a four-component copolymer of ethylene / vinyl acetate / Vinyl chloride / methacrylate ester suggested (JA-OS 38 558/77). However, those from this aqueous emulsion have produced films still have a tendency to yellow.

A process for the preparation of an aqueous emulsion has also been proposed (JA-OS 1 25 167/76), that consists in the fact that an aqueous emulsion of an ethylene / vinyl acetate copolymer or a produces an aqueous emulsion from a terpolymer of ethylene / vinyl acetate / vinyl chloride in a first stage, at least one ethylenically unsaturated compound, such as styrene, is added to the emulsion and the unsaturated one Compound emulsion-polymerized in the presence of an oil-soluble radical polymerization initiator However, technical practice occurs with any process in which a styrene monomer is used in a later stage the polymerization is added poses great difficulty. For example, it's difficult to do the whole thing to polymerize styrene added to the reaction system in the final stage, and after discharging the As a result, a small amount of styrene monomer inevitably remains in the reactor. The new copolymerization of ethylene in the first stage with vinyl acetate can not go smoothly in the reactor, in which there is still a small Amount of styrene monomer remaining can be carried out. It is well known that vinyl acetate is undesirable Has copolymerization parameters with respect to styrene and that a small amount of Styrene monomer acts as a retarder for the inhibition of the polymerization of vinyl acetate (cf. e.g. Paul J. f-jory: Principles of Polymer Chemistry, pages J87-189). A film made from the watery An emulsion obtained by such a process shows inferior transparency. Water resistance, alkali resistance and breaking strength compared to a film made from the invention aqueous emulsion has been prepared.

In contrast, according to the invention, an aqueous emulsion containing a styrene component in the Containing solids is easily made without the aforementioned difficulties in the polymerization process and the resulting aqueous emulsion has superior properties.

Preferred embodiments according to the invention are explained in more detail below that as a component (B) Styrene monomer used in the present invention includes styrene and styrene derivatives such as «-Methylstyrene, 2-chlorostyrene, 4-chlorostyrene, 2,5-dichlorostyrene and 4-methoxystyrene. Styrene is preferred. That Styrene monomers (B) mainly contributes to the water resistance and hardness of one of the aqueous Emu jion produced film.

Examples of monomers copolymerizable with the styrene monomer used together with the Styrene monomers used as required include acrylates and methacrylates [hereinafter referred to as »(Meth) Acryiate« abbreviated], such as * 4ethyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylates, unsaturated acids such as acrylic acid and methacrylic acid, Maleic acid and its esters, (meth) acrylonitriles, (meth) acrylamides, vinyl pyridine and vinyipyrrolidone. The amount on the other copolymerizable monomer is up to 3 times, preferably up to 2 times, based on the weight of the styrene monomer.

In addition, a polyolefinically unsaturated comonomer, such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, Allyl (meih) acrylate or divinylbenzene, in an amount up to 10% by weight, based on the Total amount of component (B) can be used.

The vinyl ester used as component (C) is a vinyl ester of a linear or branched carboxylic acid having 1 to 25 carbon atoms, preferably 2 to 20 carbon atoms, and comprises e.g. B. vinyl acetate, vinyl propionate, Vinyl butyrate, vinyl valerate, vinyl 2-ethylhexylate, vinyl isononanate, vinyl laurate, vinyl stearate, vinyl versatate and their mixtures.

Examples of a monomer copolymerizable with the vinyl ester are vinyl halides such as vinyl chloride and vinyl bromide, acrylic acid esters, fumaric acid esters, crotonic acid and their derivatives. The amount of such comonomer is up to 3 times, preferably up to 2 times, based on the weight of the Vinyl esters.

The solids concentration of the aqueous emulsion according to the invention is 10 to 60% by weight, preferably 30 to 55% by weight, and the solids consist of particles of a polymer or copolymer or one Mixture thereof obtained in the polymerization or copolymerization of the following components becomes: (A) 1 to 50% by weight, preferably 1 to 30% by weight; (B) 4 to 95% by weight, preferably 10 to 80% by weight, am rr are preferably 10 to 60% by weight; and (C) 4 to 95% by weight, preferably 10 to 90% by weight. The watery one Emulsion has an inherent viscosity, determined in benzene at 30 ° C., of 0.1 to 1A, preferably 0.2 to 1.

If the proportions of the individual components are outside the ranges given above, the properties of the films produced from the aqueous emulsion are influenced in various ways. If the proportion of component (A) is less than 1%, the plasticity of the film is insufficient, and if it is 50% exceeds, the film becomes too soft. When the proportion of the component (B) is below 4%, the water resistance are and the hardness of the film is insufficient, and if it exceeds 95%, the film is too hard and too brittle. If the proportion of component (C) is less than 4%, adhesiveness does not easily develop, and if it exceeds 95% by weight, the film becomes brittle or has deteriorated alkali resistance. By appropriately selecting the proportions of the individual components within the specified ranges it is possible to make films with various properties that are in the range of those that are soft and have high elongation to those exhibiting moderate elongation and strength, and from those that have strong tack to those that do not have tack. The manufactured Films are flexible and have good transparency and excellent water resistance, alkali resistance and weather resistance.

Additives such as pigments, plasticizers, antiseptics and defoaming agents can be mixed with the synthetic multicomponent resin emulsion according to the invention. The emulsion according to the invention is useful for coating, for painting, for gluing, for treating paper, for treating textiles and also as additives for cement and mortar. The multicomponent synthetic resin isolated from the aqueous emulsion of the multicomponent synthetic resin of the present invention is useful as a hot melt substrate or as an extender for synthetic resins such as polyolefins. The reference examples 1 to 5 listed below show some application examples which show the superiority of the aqueous emulsion according to the invention
The process for preparing the aqueous emulsion of the present invention will now be explained. That

The process is characterized in that it comprises a first step in which ethylene and (B) a styrene monomer or a mixture of a styrene monomer and a monomer copolymerizable therewith Formation of an aqueous emulsion which is essentially free of the monomer (B), emulsion-polymerisicn are, and a second stage in which ethylene and (C) a vinyl ester or a mixture of a vinyl ester and a monomer copolymerizable therewith in the presence of the aqueous one formed in the first stage Emulsion can be emulsion-polymerized. In order to simplify the description, the above procedure is implemented in the described in more detail below, using styrene as monomer (B) and vinyl acetate as monomer (C) will.

Normally, all of the styrene to be used is in the polymerization of the first stage Given a reactor containing an aqueous medium containing a dispersant. Ethylene is under pressure reacted with the styrene. If necessary, some of the styrene can be added at the beginning and the rest can be added in portions as the polymerization proceeds. Alternatively -; ann part of the Dispersant can be added to the reactor, and then a solution from another part of the Dispersing agent in styrene can be added. Or you can use a mixture of water, a dispersant and emulsify styrene and then add to the reactor.

In the polymerization of the first stage, it is important that the styrene is completely in the presence of ethylene is polymerized so that there is essentially no non-conversion of styrene monomer in the reaction system If the styrene monomer remains, the polymerization of vinyl acetate and ethylene will occur the second stage inhibited. In the emulsion polymerization of styrene and ethylene takes place in the first stage the reaction, the main reaction being the polymerization of styrene first, then the copolymerization

of styrene and ethylene and finally the polymerization of ethylene. So one can see the presence of Easily avoid residual styrene monomer. It was confirmed that even in a trace amount such as 300 ppm, styrene monomer remains in the aqueous emulsion formed in the first stage, which Polymerization in the second stage proceeds without difficulty. Thus, a substantial absence means of styrene monomer that it is not present in an amount above about 300 ppm.

The polymerization of the first stage is preferably carried out in such a way that the solids content of the aqueous emulsion is 5 to 60 wt .-%, preferably 5 to 40 wt .-%. If the solids content is high, the second stage polymerization is carried out after the emulsion has been diluted with water. Finally, an aqueous emulsion with a solids content of 10 to 60% by weight is prepared. the Polymerization of vinyl acetate and ethylene in the second stage is carried out in the presence of the aqueous emulsion, which has been obtained at Her first stage carried out. According to the invention, the polymerization is the second Stage carried out following the polymerization of the first stage In particular, vinyl acetate and if necessary, an additional amount of ethylene introduced into the reactor, which is the case in the first stage Contains formed, aqueous emulsion and unreacted, pressurized ethylene monomer, and then the second stage polymerization can be carried out. The second stage polymerization is carried out in the presence of the aqueous emulsion of the first stage which has been prepared separately.

The ratio between the amount of ethylene polymerized in the first stage and that of Ethylene polymerized in the second stage is not particularly limited. It is enough that the Total amount of ethylene in these stages to the desired value, d. H. 1 to 50 wt% solids, is set. In general, the introduction of vinyl acetate takes place subsequently in the presence of ethylene negative pressure. However, there are no particular restrictions.

The polymerization in the second stage is easy and very smooth, like the polymerization in the first stage. Finally, an aqueous emulsion is obtained which contains polymerized particles having an average size of 0.01 to 2 microns of the individual components in the proportions given above.
The Polymcrisulionstemperatur is 0 to 100 ⁰ C, HCV. iV.ugt 20 to 90 "C, and the polymerization pressure is in the range of 0.49 to 19.6 MPa (5 to 200 kg / cm ² ), preferably 0.981 to 9.81 MPa (10 to 100 kg / cm ² ) The pressure is generated by pressurizing the ethylene used as a raw material, In the first and second stages, the temperature and pressure may be the same or different within the above ranges.

In the present invention, emulsion polymerization is carried out a-jf in the usual manner second stage of the two-stage polymerization according to the invention, the monomers are added are, in the presence of the aqueous emulsion obtained in the first stage, successively on the Particles of the aqueous emulsion obtained in the first stage are seed-polymerized. Catalysts, dispersants, Emulsifiers and protective colloids that can be used in emulsion polymerization, are explained below.

Catalysts which initiate radicals are expediently used as the polymerization catalysts. Examples of such polymerization catalysts include potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide, Azo-b'S- (2-amidinopropane) hydrochloride, lauroyl peroxide, succinic acid butyl peroxide, ketone hydroperoxide. Λ / t'-Azo-bis-isobutyric acid ester and a / t'-Azc-bis-isobutyronitru. These catalysts can

can be used individually or as "redox catalysts" together with suitable reducing agents. Examples suitable reducing agents are amines, iron (II) salts, sodium thiosulfate, sodium sulfite, sodium hyposulfite and formaldehyde sodium sulfoxylate. The appropriate amount of catalyst and optionally reducing agent is 0.01 to 20 wt .-%, based on the total weight of the monomers. The catalyst can be added once at the beginning of the polymerization or one part can be added at the beginning and the rest at the 5th,

Continuation of the polymerization are added.

Emulsifiers or protective colloids or both normally used in emulsion polymerization can be used as dispersants.

Examples of emulsifying agents include anionic surfactants, nonionic surfactants Agents and cationic surfactants. Examples of anionic surfactants are alkyl sulfates, Alkylaryl sulfates, sulfates of hydroxyalkanols, sulfosuccinic acid esters, and sulfates and phosphates of Alkyl or alkylaryl polyethoxyalkanols. Specific examples are nonionic surfactants Polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, addition products between 5 and 50 moles of ethylene oxide and linea- '

ren or branched carboxamides with 6 to 22 carbon atoms and a block copolymer Propylene oxide and ethylene oxide. Examples of cationic surfactants include alkylamine salts, quaternaries Ammonium salts and polyoxyethylene alkylamines. A combination of a nonionic surfactant Agents having an anionic surfactant or a cationic surfactant Medium is also possible. The amount of surface-active agent is U, i to 40 oew.- ° / b, based based on the total weight of the monomer in the first stage.

Protective colloids include e.g. B. polyvinyl alcohols, such as polyvinyl alcohol, partially acetylated polyvinyl alcohol or a partially or fully saponified product of a copolymer of vinyl acetate and a (Meth) acrylate esters, water-soluble cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose or carboxymethyl cellulose, water-soluble starch, a water-soluble copolymer (Meth) acrylic acid and an amide, a copolymer of styrene and maleic acid, a copolymer of styrene and Maleimide, and a poly-N-vinyl compound made from an open-celled or cyclic carboxamide. the The amount of protective colloid is at most 20% by weight, based on the total weight of the monomers in the first stage.

During the polymerization, the pH of the reaction mixture is 2 to 8, preferably 3 to 5, held. If desired, a buffer can be used to adjust the pH. Examples of buffers are 30,

Acids such as formic acid, acetic acid, hydrochloric acid and sulfuric acid, acids such as ammonia, amines, Sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali carbonates, phosphate salts and acetic acid salts. If desired, mercaptans, aldehydes, chlorinated hydrocarbons, etc. can be used as regulating agents the molecular weight can be added.

The following examples illustrate the invention. The various properties listed in the examples are determined according to the following procedures.

(a) Tensile strength and elongation

An emulsion with a solids content of 25 wt .-% is on a polyethylene plate on a frame Poured with a predetermined area and dried in the air at room temperature for at least 48 hours. then is further dried in vacuo at room temperature for at least 24 hours until the weight is constant is. A film sample with a thickness of 0.25 ± 0.03 mm is used. A dumbbell sample with a width of 20 mm is made from the film sample, and its strength and elongation are determined according to JJS Z-1702 under Determined using a tensile tester (Toyo-Baldwin-Tensilon UTM-III-100).

(b) Alkali Resistance

A 5x5 cm sample is cut from the film to a thickness of 0.25 + 0.03 mm and up to Constant weight as in (a) above, dried. The sample is immersed in a 25% aqueous solution of 0 for 4 days Immersed in sodium hydroxide, then it is immersed in distilled water for 1 day, from the distilled Water removed and dried to constant weight. The weight loss is expressed as a percentage of the

Weight of the film? expressed and defined as the alkali resistance of the film ■

(c) Water resistance 55 ^

The 5 × 5 cm film sample, described in (b), is immersed in distilled water for 24 hours

Before adhering water is wiped off with a paper towel. The film is then weighed and the weight is removed

weight increase is defined as water resistance {%) i,

(d) Logarithmic viscosity $

The inherent viscosity is determined by a benzene solution with a polymer concentration of 0.4 g / dl 30 ° C determined using a Cannon-Fenske viscometer. The inherent viscosity is determined from calculated from the following equation: "

loearithmic viscosity =

where η _{Γ is} the viscosity ratio and c is the concentration (g / dl) of the polymer.

Example i

The following are placed in a 1 l stainless steel autoclave equipped with an anchor stirrer Components.

distilled water 298

Polyoxyethylene nonylphenol ether 9.6

Sodium Lauryl Sulphate 2.4

Sodium pyrophosphate 2.0

Ammonium persulfate 2.0

Styrene 86

The air inside the autoclave is sufficiently decomposed by nitrogen and ethylene. Under stirring, the polymerization temperature is raised to 7O ⁰ C, and the pressure of ethylene is (kg / cm ² 45) is increased to 4.41 MPa. In this state, the first-stage polymerization is carried out for 3.5 hours. Then 200 g of vinyl acetate are added in the course of 2 hours and the polymerization of the second stage becomes

continued. Since ethylene was not additionally added during this time, the pressure of ethylene decreases from 4.41 MPa (45 kg / cm ² ) to 3.1 MPa (32 kg / cm ² ). If the polymerization is continued for 1.5 hours, the ethylene pressure decreases further to 2.5 MPa (26 kg / cm ² ). The autoclave is then allowed to cool and the product is removed. The resulting aqueous emulsion of a multicomponent synthetic resin is a stable blue-white emulsion with an average particle diameter of less than 0.1 microns and a plastic content of 4937% by weight.

A bluish film with flexibility at room temperature and good transparency becomes the wäürigcn Synthetic resin emulsion obtained. The film contains 3.30% by weight of ethylene. 65.65% by weight vinyl acetate, 31.06% by weight styrene and has the following properties:

Alkaline ^: resistance 1.77%

Water resistance 19.45%

Breaking strength 466 N / cm ²

Elongation 540%

inherent viscosity 0.46

Comparative example 1

The same autoclave as used in Example 1 is charged with the same components as used in Example 1. The air inside the autoclave is then completely replaced by nitrogen, and the first polymerization stage is carried out at 70 ° C. for 3.5 hours while ^{stirring under a nitrogen pressure of 5.3 MPa (54 kg / cm 2).} After the polymerization of the first stage has ended, the nitrogen is released. Then 3.1 MPa (32 kg / cm ² ) ethylene are fed in, and 200 g $

Vinyl acetate are added over the course of 2 hours, the polymerization of the second stage being carried out £

will. Since no additional ethylene is introduced during this time, the pressure falls from 3.1 MPa (32 kg / cm ² ) to 2.8 M Pa (29 kg / cm ² ). In this state, the polymerization is continued for 1.5 hours.

After the autoclave has been allowed to cool, the product is removed. The product is an emulsion with has a strong odor of vinyl acetate and has a solids concentration of 18.09% by weight. The firm one Part of the emulsion is a homopolymer made from styrene. Vinyl acetate and ethylene are not polymerized, lie however, dissolved in the aqueous emulsion as monomers.

Comparative example 2
The following ingredients are added to the same autoclave as used in Example 1.

G

Distilled Water 298

Polyoxyethylene nonylphenol ether 9.6

Sodium Lauryl Sulphate 2.4

Sodium pyrophosphate 2.0

Ammonium persulfate 2.0

Thereafter, the air inside the autoclave is completely replaced by nitrogen and ethylene with stirring by increasing the polymerization temperature to 70 ⁰ C and the ethylene pressure to 4.4 MPa (45 kg / cm ^2). A monomer mixture of 200 g of vinyl acetate and 86 g of styrene is added over the course of 5.5 hours. During this time, no additional ethylene is introduced. After the monomer mixture has been added, the polymerization is continued in this state for 1.5 hours. The autoclave is allowed to cool and the product is removed. The product is an emulsion with a strong vinyl acetate odor and contains 19.24 weight percent solids. The solids are homopolymers of styrene. Vinyl acetate and styrene are not polymerized at all

'fj example 2

The same autoclave as used in Example 1 is charged with the following ingredients.

i; Distilled water 540

| ί Polyethylene glycol monomethacrylate 1.5

S | Polyoxyethylene nonylphenol ether 9.6

IJ sodium pyrophosphate 3.0

£ ammonium persulphate 3.0 to

V styrene 28.5

i \ Subsequently, the air inside the autoclave was replaced by nitrogen and ethylene. While stirring

; the polymerization ^{temperature is set to 70 0} C and the ethylene pressure is increased to 4.9 MPa (50 kg / cm ² ).

In this state, the polymerization of the first stage is carried out for 3.5 hours. Then 210 g

tp. Vinyl acetate introduced in the course of 2 h and the polymerization of the / wide stage is carried out. While

During this time no additional ethylene is added, and therefore the ethylene pressure drops from 4.9 M Pa (50 kg / cm ³ )

Vv to 2.99 MPa (30.5 kg / cm ² ). After the addition of vinyl chloride, the polymerization for 1 h at 70 ⁰ C weitergc-

JH leads. The Äinyieiiuiuck uc-ügt 2.2 MPa (22.5 kg / cm ² ). The properties of the resulting aqueous emulsion

■ j <i made of synthetic resin and a film made therefrom are shown in Table 1.

S B e i s ρ i e 1 3

T The two-stage polymerization is carried out under the same conditions as in Example 2, with the

Exception that in the first stage the amount of styrene is changed to 57.0 g and the amount of polyethylene glycol monome- ■ thacrylate is changed to 3.0 g. The properties of the resulting aqueous emulsion from synthetic

j Resin and a film made from it are listed in Table 1.

t example 4

I -

£ j The two-stage polymerization is carried out under the same conditions as in Example 2, with the

k Exception that in the first stage the amount of styrene to 85.5 g and the amount of polyethylene glycol monome-

t; thacrylate is changed to 4.5 g. The properties of the aqueous synthetic resin emulsion and one

I films made therefrom are shown in Table 1.

I.

II Example 5

H The two-stage polymerization is carried out under the same conditions as in Example 2, with the

Except that in the first stage the amount of styrene to 114.0 g and the amount of polyethylene glycol monomethacrylate was changed to 6.0 g. The properties of the aqueous emulsion of synthetic resin and of a film made therefrom are shown in Table 1.

Comparative Example 3 The same autoclave as used in Example 1 is charged with the following ingredients.

Distilled Water 298

Polyoxyethylene nonylphenol ether 9.6

Sodium Lauryl Sulphate 2.4

N atrium pyrophosphate 1 2

Ammonium persulfate 0.9

The air inside the autoclave is then replaced by nitrogen and ethylene. The temperature is set to 70 ^° C. with stirring. Ethylene is then passed in up to a pressure of 43 MPa (50 kg / cm ² ). Then 286 g of vinyl acetate are added in the course of 3 hours to carry out the copolymerization. During this time the ethylene pressure is maintained at 43 MPa (50 kg / cm ² ). After the addition of vinyl acetate, the polymerization temperature is raised to 8O ⁰ C and the polymerization is carried out 1 h the autoclave was allowed to cool and unreacted ethylene is relaxed The reaction product is removed. The properties of the resulting aqueous emulsion of ethylene / vinyl acetate copolymer and a film made therefrom are shown in Table 1.

Table 1

Example 2 Example 3 Example 4 Example 5 Comp.-B. 3

Properties of the emulsion Solids concentration (% by weight) pH

Particle diameter (microns) inherent viscosity

Properties of the film Ethylene content (% by weight) Vinyl acetate content (% by weight) Styrene content (% by weight) 15 Water resistance (%) Alkali resistance (%) Breaking strength (N / cm ² (kg / cm ² )) Elongation (%)

B e i s ρ i e i 6

The same autoclave as used in Example 1 is charged with the following ingredients.

33.73 36.17 38.05 39.21 4 ^ .23 4.70 4.60 4.75 4.70 4.70 below 0.1 below 0.1 below 0.1 below 0.1 038 0.498 0.465 0.448 0.447 0.411 14.76 14.07 05/12 9.58 17.25 73.20 66.10 60.51 55.51 82.70 11.44 18.84 07/26 33.16 - 22.14 20.29 18.53 15.69 33.80 6.53 4.80 4.28 7.19 12.20 59 (6.01) 95 (9.71) 188 (19.16) 412 (42.12) 19 (2.04) > 1400 > 1400 1303 588 > 1400

25 Distilled water

Polyvinyl alcohol

Polyoxyethylene nonylphenol ether

Sodium lauryl sulfate

Sodium pyrophosphate 30 ammonium persulfate

Styrene

297.8 1.2 9.6 2.4 2.0 2.0 86

The air inside the autoclave is then replaced by nitrogen and ethylene. The polymerization temperature is adjusted to 70 ° C. with stirring and the ethylene pressure is increased to 4.4 MPa (45 kg / cm ² ).

y, In this state, the first-stage polymerization is carried out for 2 hours. 200 g of vinyl acetate are then passed in over the course of 2 hours and the polymerization of the second stage is carried out. During this time no additional ethylene is added, and therefore the ethylene pressure falls from 4.4 MPa (45 kg / cm- ') to 3.1 m over (34 kg / cm ² ), in this state the polymerization is continued for 2 hours. The autoclave can then cool down and the product is removed. The properties of the resulting aqueous emulsion of synthetic resin and a film made therefrom are shown in Table 2.

Example 7

The two-stage polymerization is carried out under the same conditions as in Example 6, with the Exception that 3 g of hydroxyethyl cellulose are used instead of polyvinyl alcohol. The properties of the resulting synthetic resin emulsion and a film made therefrom are shown in Table 2 listed.

Comparative example 4
The same autoclave as used in Example 1 is charged with the following ingredients.

Distilled water

Hydroxyethyl Cellulose (AL-15)

Polyoxyethylene nonylphenol ether

Sodium lauryl sulfate

Sodium pyrophosphate

Ammonium persulfate

307.5 3.5 9.6 9.6 U 0.6

The air inside the autoclave is then replaced by nitrogen and ethylene. With stirring, the polymerization temperature is set to 70 ° C. and the ethylene pressure is maintained at 3.4 MPa (35 kg / cm ² ). Then 300 g of vinyl acetate are passed in over 3 hours and copolymerized with ethylene. During this time the ethylene pressure is maintained at 3.4 MPa (35 kg / cm ² ). After the addition, the polymerization ^{temperature is increased to 80 °} C. and the polymerization is continued for a further hour. The autoclave is allowed to cool and the ethylene is released. The product is then removed. The properties of the resulting emulsion of ethylene / vinyl acetate copolymer and a film produced therefrom are listed in Table 2

Comparative example 5

A 500 ml four-necked flask fitted with a thermometer, stirrer, nitrogen; nla3rohr, reflux condenser and The dropping funnel is equipped with the following components.

5 g

Ethylene / vinyl acetate copolymer obtained in

Comp.-B. 4 (the solids concentration becomes

using water to 44.5% by weight

set) 100

Na ₂ SO ₃ - 7 H ₂ O 0.25

distilled water 13.7

The air inside the flask is replaced with nitrogen. While nitrogen is slowly flowing in, the flask is heated with stirring. When the temperature inside has reached 60 ⁰ C, 223 g of styrene containing 0.1? Benzoyl peroxide was added dropwise over the course of 1 h. During this time, the polymerization temperature is kept at 60 ° C. After the addition, the polymerization for 1 h and 20 continued at 60 ⁰ C min The resulting emulsion has a slight smell of styrene, and a film produced from the emulsion is white and completely opaque. The other properties of the emulsion and the film are shown in Table 2

Comparative example 6
The same autoclave as used in Example 1 is charged with the following ingredients.

S.

Distilled water 307.5

Hydroxyethyl cellulose 3.5

Polyoxyethylene nonylphenol ether 9.6

Sodium Lauryl Sulphate 9.6

Sodium pyrophosphate 1,2

Ammonium persulfate 0.6

The air inside the autoclave is then replaced by nitrogen and ethylene. The polymerization temperature is adjusted to 70 ° C. and the ethylene pressure to 3.4 MPa (35 kg / cm ² ) with stirring. Over the course of 23 hours, 255 g of vinyl acetate are added and the mixture is copolymerized with ethylene. After the addition of the vinyl acetate, 45 g of methylene methacrylate (MMA) are introduced and polymerized over the course of 30 minutes. During this time the ethylene pressure is maintained at 3.4 MPa (35 kg / cm ² ). After the addition, the polymerization temperature is raised to 8O ⁰ C, and the polymerization is continued for 1 hour. The autoclave can cool down and ethylene is depressurized. The reaction product is taken out. The resulting emulsion smells strongly of unreacted methyl methacrylate. The properties of the resulting emulsion and a film made therefrom are shown in Table 2.

Example 8

The two-stage polymerization is carried out under the same conditions as in Example 1, with the Exception that in the first stage a monomeric mixture of 43 g of styrene and 43 g of methyl methacrylate instead of 86 g of styrene is used. The properties of the resulting aqueous emulsion of synthetic Resin and a film made therefrom are shown in Table 2.

Example 9

The two-stage polymerization reaction is carried out under the same conditions as in Example 1, with the exception that a monomeric mixture of 77.4 g styrene and 8.6 g acrylonitrile (AN) instead of 86 g of styrene is used. The properties of the resulting aqueous synthetic resin emulsion and a film made therefrom are shown in Table 2.

Example 10

The same autoclave as used in Example 1 is charged with the following ingredients.

Distilled water 540

Polyoxyethylene nonylphenol ether 9.6

Sodium pyrophosphate 3.0

Ammonium persulfate 3.0

Styrene 30

Then, the air inside the autoclave is completely replaced by nitrogen and ethylene with stirring by increasing the polymerization temperature to 70 ⁰ C and the ethylene pressure at 7.45 MPa (76 kg / cm ^2). In this state, the polymerization of the first stage is carried out for 3.5 hours. The autoclave can then cool and the ethylene is let down. The product is removed. The resulting, aqueous emulsion made of synthetic The resin is a stable emulsion with an average particle diameter of less than 0.1 microns and a solids content of 8! 0% by weight. It is free from a styrene odor. However, if this aqueous emulsion is dried at room temperature, it breaks into white, semi-transparent pieces with an average area of about 5 mm ² . You don't get a movie. The solids content consists of 91.0% by weight of styrene and 9.0% by weight of ethylene.

ίο the following polymerization as the second stage carried out, the autoclave used in the first stage is treated with 100 g of distilled water charged Subsequently, the air inside the autoclave is completely replaced by nitrogen and ethylene with stirring by increasing the polymerization temperature to 70 ⁰ C and the ethylene pressure to 736 MPa (75 kg / cm ² ). Then 580 g of the styrene / ethylene copolymer emulsion prepared in the first stage, 210 g of vinyl acetate and 3.0 g of ammonium persulfate are added under a stream of nitrogen Room temperature to produce a pre-emulsion stirred vigorously The pre-emulsion is added to the autoclave and polymerized over the course of 2 hours. During this time, no additional ethylene is introduced and therefore the ethylene pressure falls to 4.71 MPa (48 kg / cm ² ) . If the polymerization is continued 1 h after the pre-emulsion has been mixed, the ethylene pressure falls further to 3.5 MPa (36 kg / cm ² ). The autoclave can then cool down and the product is removed. The properties of the resulting aqueous emulsion synthetic resin and a film made therefrom are shown in Table 2

Example 11

The two-stage polymerization is carried out under the same conditions as in Example 1, with the exception that 3.0 g of azo-bis (2-amidinopropaii) hydrochloride instead of 2.0 g ammonium persulfate used does not use Natriumpyiophosphat, keeping the reaction temperature at 60 ⁰ C. The properties of the resulting aqueous synthetic resin emulsion and a film made therefrom are shown in Table 2

Table 2

Example 6 Example 7 Comp.-B.4 Comp.-B.5 Comp.-B.6 Properties of the emulsion
Solid conc. (Wt .-%)
pH
Particle diameter (microns)
log. viscosity 49.22
430
below 0.1
0.489 49.93
4.70
below 0.1
0351 52.19
4.70
0.73 4836
4.70
0.78 49.60
4.62
0.70 Properties of the film
Ethylene content (wt .-%)
Vinyl acetate content (% by weight)
Styrene content (wt%)
Content of with styrene
copolymerizable monomer
(Wt .-%)
Water resistance (%)
Alkali resistance (° / o)
Breaking strength (N / cm ² (kg / cm ² ))
Strain(%) 430
63.92
31.79 4.15
64.71
31.14 1430
85.70 13.18
54.62
32.20 1230
7630 I.
11.40 (MMA) 1 8.85
1.95
584 (59.55)
425 19.88
3.71
740 (75.48)
470 30.60
4.00
34 (4.5)
> 1400 27.84
5.72
105 (10.74)
775 4730 1
7.60 %
314 (32.2) M.
700 I. 1

Table 2 (continued)

Example 8 Example 9 Example 10 Example 11 G
310 Properties of the emulsion 9.6 Solids concentration. (Wt .-%) 46.80 47.55 30.45 4933 2.4 pH 430 4.05 4.12 3.12 U Particle diameter (microns) below 0.1 under C.l below 0.1 below 0.1 05 log. viscosity 0305 0.582 0.476 0.633 Properties of the film Ethylene content (wt .-%) 10.26 3.26 15.23 530 Vinyl acetate content (% by weight) 61.62 63.80 72.70 63.60 Styrene content (wt.%) 14.03 29.28 12.07 31.02 Content of with styrene 14.09 (MMA.) 3.66 (AN) - - copolymerizable monomer (wt%) Water resistance (%) 23.44 19.13 25.65 18.86 Alkdi resistance (%) 154 337 138 157 Breaking strength (N / cm ² (kg / cm ² )) 117 (12.63) 598 (6039) - - Strain(%) 1417 458 - - Comparative example 7 The same autoclave as used in Example 1 is charged with the following ingredients. Distilled water Polyoxyethylene nonylphenol ether Sodium lauryl sulfate Sodium pyrophosphate Ammonium precipitate

The air inside the autoclave is then replaced by nitrogen and ethylene. While stirring, the temperature inside the autoclave is increased to 70 ^° C. and ethylene is passed in. The ethylene pressure increases to 2.2 MPa (23 kg / cm ² ). 300 g of vinyl acetate containing 1.5 g of triallyl cyanurate are then added over the course of 3 hours and copolymerized. During this time, the ethylene pressure is kept at 2.2 MPa (23 kg / cm ² ). After the addition, the polymerization temperature is raised to 8O ⁰ C, and the polymerization is continued for 1 hour. The autoclave is allowed to cool and the ethylene is depressurized. The reaction product is removed. The properties of the resulting ethylene / vinyl acetate emulsion and a film produced therefrom are listed below

Solids concentration 48.20% by weight

pH 335

Particle diameter 0.25 microns

Ethylene content 8.44% by weight

Vinyl acetate content 90.86% by weight

Water resistant wedge 3334%

Alkali resistance 6.0%

Breaking strength 461 N / cm ² (47.41 kg / cm ² )

Elongation 475%

te 50 g of the resulting emulsion are mixed with 130 g of the ethylene /

Styrene copolymer emulsion mixed to form an emulsion mixture. One from the emulsion mix The film produced is white and semi-transparent and has the following properties.

Water resistance 35.22%

Alkali resistance 6.20%

Breaking strength 340 N / cm ² (34.65 kg / cm ² )

Elongation 350%

It is clear from the above values that mere blending of water resistance and Alkali resistance not improved and a reduction in both breaking strength and elongation causes.

Example 12
The same autoclave as used in Example 1 is mixed with the following ingredients

G

Distilled water 268 10% aqueous solution of

Hydroxyethyl cellulose 30

Polyoxyethylene nonylphenol ether 9.6

to sodium lauryl sulfate 2.4

Sodium pyrophosphate 2.0

Ammonium persulfate 3.5

Styrene 86

The air inside the autoclave is then replaced by nitrogen and ethylene. While stirring, the temperature inside the autoclave is increased to 70 ° C. and the ethylene pressure to 7.85 MPa (80 kg / cm ² ). In this state, the polymerization of the first stage is carried out for 2 hours. A monomeric mixture of g vinyl acetate and 100 g vinyl chloride is added over 6 hours in the second stage and polymerizes. During this time, the ethylene pressure is 7.85 MPa (80 kg / cm ² ) held,

After the addition of the monomeric mixture, the further addition of ethylene is stopped and the polymerization takes place for 8 hours. The autoclave can cool down and ethylene is depressurized. The reac onsprodukt is taken. The properties of the resulting aqueous synthetic resin emulsion apply to one of them produced films are listed below

Solids concentration 48.65% by weight

pH 3.80

Particle diameter less than 0.1 micron

Ethylene content 11.02% by weight

Vinyl acetate content 28.22% by weight

Vinyl chloride content 29.02% by weight

Styrene content 31.06% by weight

Water resistance 1430%

Alkali resistance 3.66%

Breaking strength 781.8 N / cm ² (79.72 kg / cm ² )

Elongation 483%

Example Ί3
The same autoclave as used in Example 1 is charged with the following ingredients

Distilled Water 298

Polyoxyethylene nonylphenol ether 9.6

Sodium Lauryl Sulphate 2.4

Sodium pyrophosphate 2.0

A. ammonium persulfate 2.0

Styrene 43

Methyl methacrylate 43

After that, the air inside the autoclave is completely replaced by nitrogen and ethylene. With stirring, increasing the Polymerisalionstemperatur to 70 ⁰ C and the Äthylrndruck to 7.85 MPa (80 kg / cm ^2). In this state, the polymerization of the first stage takes place for 2.5 hours.

A monomeric mixture of 100 g of vinyl acetate and g of vinyl chloride is then added over the course of δ h and polymerized as the polymerization of the second stage. During this time the ethylene pressure is maintained at 7.85 MPa (80 kg / cm ² ). After the addition of the monomeric mixture, the fresh addition of ethylene is stopped and the polymerization is carried out for 6 hours. After the polymerization, the autoclave can cool down and the ethylene is depressurized. The reaction product is taken out. The properties of the aqueous emulsion of multicomponent synthetic resin and a film made therefrom are shown below

Solids concentration 4922% by weight

pH 3.80

Particle diameter less than 0.1 micron

Ethylene content 10.88% by weight

Vinyl acetate content 28.53% by volume

Vinyl chloride content 28.67% by weight

Styrene content 14.40% by weight

MMA content 15.03% by weight

Water resistance Alkali resistance breaking strength elongation

14.72% 2.88% 689 N / cm ² (70.33 kg / cm ² ) 522%

The following reference examples show some application examples of the aqueous emulsion according to the invention.

Reference example I.

A water-based paint vchiculum of the following formulation is prepared using the aqueous emulsion obtained in Example 1 made of synthetic multicomponent resin.

Recipe for the paint carrier

Water ethylene glycol 2-methyl-2,4-dentanediol 10% sodium hexametaphosphate Dispersing agent (10%) ammonia water, polyoxyethylene nonylphenyl ether Anti-mold agent Antifoam agent Methyl cellulose (2%) Titanium oxide Calcium carbonate volume

Mica emulsion (50%) in total

PVC (pigment volume concentration)

Parts by weight

1.0

0.2 15.0 12.0 24.0 10.5 2.0 24.0 (12.OaIs solids) 100.4 parts by weight

60%

Using the above vehicle, a sand finish paint of the following formulation is prepared. Recipe of sand line painting agent

Parts by weight Paint carrier 100 white marble (average diameter 1.5 mm) 50 white marble (average diameter 1 mm) 50 all in all 200 parts by weight

The sand finish paint is applied to flexible cardboard using a spray gun with a pneumatic spray pressure of 0.49 MPa (5 kg / cm ² ) and an inner diameter of 6 mm in a wet amount of 100 g / cm ³ at a distance between the gun and the cardboard sprayed on about 50 cm. The applied paint is dried for 7 days, and then the water resistance, alkali resistance and weather resistance of the resulting applied paint are measured by the following methods.

Water resistance

A test sample is immersed in water for 4 days and the hardness and swelling of the coated surface is 5: marriages are rated on a scale with five ratings, with 5 being the best and 1 being the worst Condition means

Alkali resistance

A test sample is immersed in a saturated aqueous solution of calcium hydroxide for 4 days and then the hardness and swelling of the coated surface are rated on a scale with five ratings where 5 is the best condition and 1 is the worst condition.

Weather resistance

A test sample is exposed to a Weather-O-Meter for 50 hours and / JE, the crack pattern, and swelling of the coated surface are observed. ΔΕ = color difference (NBS unit) The results are shown in Table 3.

Table 3 Reference example 1

comparison 1*)

4th
5 3
4th 3.5
4.5 4th
4.5 3
3.5 3.5
4th 2.3
no 4.4
no 3.2
no

Water resistance hardness sources

Alkali resistance hardness sources

20 Resistance to weathering (resistance to soiling) ΔΕ cracking, swelling

minimum film formation temperature ("C)

*) Reference example 1 is repeated, with the exception that a commercially available ethylene / vinyl acetate copolymer

Emulsion with an ethylene content of 12 wt .-% is used as an aqueous starting emulsion.

**) Reference example 1 is repeated, with the exception that a commercially available styrene / butyl acrylate copolymer emulsion (styrene content 50% by weight) is used as the aqueous starting emulsion.

Reference example 2

Paper is made using the aqueous emulsion obtained in Example 1 in the following manner treated with synthetic multicomponent resin.

20 g of unbleached kraft pulp are added to 980 g of water and the mixture is stirred for 2 minutes. Then, a 5% aqueous solution of sodium hydroxide is added dropwise to adjust the pH of the slurry to 8-9. The aqueous multicomponent synthetic resin emulsion (15 g) is added and then the slurry is stirred for an additional 3 minutes. Then 60 g of a 5% alum solution are gradually added as a precipitant and the mixture is stirred for 8 minutes. The slurry is then processed into paper with a Tappit machine and air-dried in a vertical dryer while still adhering. The paper is then passed twice through hot rollers at 120 ^° C. and 0.59 MPa (6 kg / cm ² ) for its heat treatment. A modified sheet of paper is obtained.

As a control, a modified paper sheet is used in the same manner as in Reference Example 2 the ethylene / vinyl acetate copolymer emulsion prepared in Comparative Example 3.

The properties of the modified papers are listed in Table 4. Those listed in Table 4 Properties are determined in the following way.

(a) thickness

The thickness of the sample in five places is measured with a micrometer, and the average thicknesses are defined as the thickness of the sample

(b) tensile strength

Determined according to a test method for the tensile strength of paper according to JIS P-8113.

(c) Wet tensile strength

Measured according to the test method for the wet tensile strength of paper and paperboard, viz J1SP-8135.

(d) Burst Strength

Measured according to the paper and paperboard burst strength test method of JIS P-8112 by means of a Muellen burst strength tester.

14th

Reference example 2 control 0.15 0.14 49.7 38.5 29.32 8.3 3.86 0.92 124 (12.63) 91 (9.31) OOAC

(e) Wrinkle Resistance

Measured according to the Test Method for the Wrinkle Resistance of Paper and Paperboard with a MIT type test equipment conforming to JIS P-8115.

(f) Degree of arbitration
Determined according to JIS P-8122.

Table 4

Thickness (mm)

Degree of arbitration (see) 49.7 38.5

Tensile strength (kg / 15 mm)

Wet tensile strength (kg / 15 mm)

Burst strength (N / cm ² (kg / cm ² ))

rüiiucSidfiuigKcii yi ^ auij

Reference example 3
Preparation of emulsion A (process according to the invention)

The following are placed in a 1 liter stainless steel autoclave equipped with an anchor stirrer Components.

Distilled Water 298

Styrene 86

Polyoxyethylene nonylphenol ether 9.6

Sodium Lauryl Sulphate 2.4

Sodium pyrophosphate 2.0

Ammonium persulfate 2.0

The air inside the autoclave is then replaced by nitrogen and ethylene. While stirring, the temperature inside the autoclave is adjusted to 70 ° C. and the ethylene pressure is increased to 4.41 MPa (45 kg / cm ² ). In this state, the first-stage polymerization is carried out for 3.5 hours. Then 200 g of vinyl acetate are added over the course of 2 hours and the polymerization of the second stage is carried out. During this time the ethylene pressure is maintained at 4.41 MPa (45 kg / cm ² ). Then the supply of ethylene is stopped and the polymerization is carried out for 1.5 hours. During this period falls on the Athylendruck * of 4.41 (4Z) to 3.73 MPa (38 kg / cm ^2). The autoclave is then cooled and the product removed. The resulting aqueous emulsion of synthetic multicomponent resin is a blue-white, stable emulsion with an average particle diameter of less than 0.1 microns and a solids content of 50.39% by weight.

The solid part of the emulsion consists of 933% by weight of ethylene, 60.67% by weight of vinyl acetate and 30.0% by weight Styrene; it has an inherent viscosity of 0.46.

Preparation of emulsion B (not according to the invention)

The same 1-1 autoclave used in making Emulsion A above is used with the the following components

Distilled water 260

Polyoxyethylene nonylphenol ether 7.2

Sodium Lauryl Sulphate 1.8

Sodium pyrophosphate 1,2

Ammonium persulfate 0.6

Hydroxyethyl cellulose 27

Subsequently, the air inside the autoclave was replaced with nitrogen and ethylene, with stirring, increasing the temperature inside the autoclave at 70 ⁰ C and the Athylendruck to 234 MPa (30 kg / cm ^2). 300 g of vinyl acetate are then added in the course of 3 hours and polymerized. After the addition, the supply of ethylene is stopped and the polymerization is continued for 2 hours. After the reaction, the autoclave is cooled and the emulsion formed is removed.

The resulting emulsion has an average particle diameter of 0.53 microns and one Solids content of 5039% by weight. The solid part of the emulsion consists of 11.76% by weight of ethylene and 88.24 % By weight vinyl acetate and has an inherent viscosity of 0396.

100 parts by weight of ordinary Portland cement, 300 parts by weight of sand and 20 parts each of the emulsions obtained A and B and an appropriate amount of water are kneaded to form a cement mixture. Test samples are made from the cement mix.

The various tests listed in Table 5 are carried out using the test samples that are aged in a dry state for 28 days, or those that are aged in water for 28 days. The results are shown in Table 5.

The method for preparing the polymer cement mortars in Reference Example 3 and Comparative Example and the procedures for testing them are the same as the physical test procedures for cement in accordance with JIS R-5201 and the test procedure for cement waterproofing agents for buildings corresponds to) IS A-1404.

Table 5

Bc / ugsbeisp. 3

control

used emulsion

MnrtpjflipRu / prt in after 30 min)

Tensile strength (N / cm ² (kg / cm ² )) dried in water

25 Flexural strength (N / cm ² (kg / cm ² )) dried in water

Compressive strength (N / cm ² (kg / cm ² )) 30 dried in water

Adhesive strength (N / cm ² (kg / cm ² )) dried in water

(compared to ordinary cement mortar)

Water absorption (%) dried

Impact strength (cm) (breaking height) dried

Dried Abrasion Resistance (mg) (Taber Index)

A.
155 B.
130 359 (36.6)
233 (23.8) 290 (29.6)
201 (20.5) 706 (72.1)
460 (46.8) 510 (52.1)
292 (29.8) 1687 (172)
2168 (221) 1648 (168)
1912 (195) 257 (26.2)
101 (10.3) 191 (19.5)
70.6 (7.2)

9.6

120

235

Reference example 4

Using each of Emulsion A obtained in Reference Example 3 and the ethylene / vinyl acetate copolymer emulsion (which is referred to as Emulsion C) obtained in Comparative Example 7 are adhesively bonded, composite structures made under the following bonding conditions by placing a sheet of plywood is glued to a semi-hard polyvinyl chloride board, a plywood board to an aluminum foil is glued, a semi-hard polyvinyl chloride plate with a cloth (cotton poplin cloth), a polyethylene terephthalate film is glued with a cloth (cotton poplin cloth).

The substrates used are as follows

Plywood sheet

A water-resistant plywood with a thickness of 5.5 mm and classified as Class 1, Quality 1 by the Japan Association of Insepcting Plywood (JAS) is cut into pieces with a size of 5 cm × 20 cm. The pieces are brushed well to remove dirt and dust on their surface and then left to stand for a day and night in a chamber kept at a constant temperature of 20 ^° C. and a relative humidity of 60%.

Semi-durable polyvinyl chloride sheet

For gluing with the plywood, a rectangular piece with a width of 25 mm and a length is used of 20 cm cut from the plate with a thickness of 0.05 mm. For gluing with a cloth, a Pieces with a size of 10 cm χ 20 cm cut out of the plate with a thickness of 0.05 mm.

Aluminum foil

For gluing with a sheet of plywood, a rectangular piece with a width of 25 mm and a Length of 20 mm cut from a film with a thickness of 0.05 mm. For gluing with a cloth it will be like this a piece with a size of 10 cm χ 20 cm cut out of a foil with a thickness of 0.05 mm.

cloth

A piece measuring 10 cm × 20 cm is cut off.

Polyethylene terephthalate

A piece with a size of 10 cm × 20 cm is cut out from a film with a thickness of 0.1 mm.

Manufacture of the bonded structure from plywood and the semi-hard polyvinyl chloride plate or the aluminum foil

The solid concentrations of the respective emulsions A and C are adjusted to 50% by weight, and these are applied to the plywood using an applicator having a thickness of 0.15 mm and a width of 30 mm and 1 minute in a constant temperature device dried at 8O ⁰ C. Then the semi-hard polyvinyl chloride plate or the aluminum foil is glued to the plywood using a hand roller. The resulting structure is left to stand ^{for 48 h in a chamber with a constant temperature, which is kept at 20 °} C. and a humidity of 60% the adhesive strength in normal state and in water and the heat resistance were measured. The results are shown in Table 6

Manufacture of a bonded composite material from cloth and the semi-hard polyvinyl plate or the polyethylene terephthalate film

The solids contents of the respective emulsions A and C are adjusted to 50% by weight. They are each applied to a semi-hard polyvinyl chloride plate and an aluminum foil using an applicator with a thickness of 0.15 mm and a width of 60 cm. Immediately afterwards, the cloth is placed on the coated layer and glued with a hand roller. The resulting structure is kept for drying for 48 hours in a constant temperature chamber, which is kept at a temperature of 20 ^° C. and a humidity of 60%, and then cut into rectangular pieces with a width of 25 mm. The adhesive strength of this sample in the normal state is shown in Table 6. The properties described above are determined according to the following methods.

45 Adhesion strength in normal condition

The bonded composite is 48 h in a constant temperature chamber held at a temperature of 2O ⁰ C and a humidity of 60%, allowed to stand and the adhesion strength is determined using a Zugtestmeßgerät (Toyo-BaldwinTensilon UTM-IIl-100).

Adhesion strength in water

The bonded composite is 48 h in a constant temperature chamber held at a temperature of 2O ⁰ C and a humidity of 60%, allowed to stand and then 12 immersed in water (20 ⁰ C) h. The adhesive strength of the bonded composite material is measured by using the same tensile tester as used in the measurement of the adhesive strength in the normal state.

Heat resistance

The bonded composite material as the plywood and the semi-hard polyvinyl chloride board is used, and a part of the upper end of the semi-hard polyvinyl chloride board is peeled off. A load of 500 g is applied to its tip. The composite material is then heated in an oven with circulating air at a rate of 10 ^° C./minute from 40 ^° C. and the temperature required for the top of the polyvinyl chloride sheet to come off and creep along a length of 25 mm certainly. This temperature is defined as the heat resistance temperature.

29 37 268 Table 6 Reference example 4 control C. in the hands; Cattle component resin dried Reference example 5 Elongation are determined The A. available normal asphalt Type of emulsion used A Type of emulsion used the mixture is stirred. Time required for mixing (min) (1) 5 5 glued composite material made of plywood and 3.0 see the softening point, the degree of penetration and the time required Degree of penetration (25 ° C) (2) 53 control semi-hard polyvinyl chloride board 4.5 2.1 Results are shown in Table 7 Softening Point (° C) (3) 54 - B. Adhesion strength in normal condition (kg / 25 mm) 3.7 68 Table 7 Elongation (cm) (15 ° C) (4) 95 10 Adhesion strength in water (kg / 0.25 mm) 78 55 57 Heat resistance (° C) 4.2 50 49 10 glued composite material made of plywood and aluminum foil 5.5 U 60 64 Adhesion strength in normal condition (kg / 25 mm) 4.7 (1) using a 500 ml beaker; Stirring speed 200 rpm; Asphalt temperature 16O ⁰ C; Adhesion strength in water (kg / 25 mm) (2) according to JIS K2530-60; 25 ° C. 100 g, 5 seconds: bonded composite material made of cloth and 0.6 (3) according to JIS K253I-60: 15th semi-hard polyvinyl chloride 1.2 (4) according to JIS K2533-71; 15 ° C, 5 cm / min. Adhesive strength in normal condition (kg / 25 mm) 0.4 bonded composite material made of cloth and mylar film 03 20th Adhesive strength in normal condition (kg / 25 ram) Control described in Reference Example 4 Reference example 5 Emulsion B will be coagulated, washed and made into a solid, synthetic The emulsion A obtained according to Reference Example 3 and the as net The synthetic resin (5% by weight) is 95% by weight of 25th (Degree of penetration 40 to 60) mixed, ^{heated to 160 c} C and then 30th 35 40 45
50

18th

Claims (1)

Patent claims: 1. Aqueous emulsion, characterized in that it contains 10 to 60 wt .-% solids from the polymerization of
5 (A) Ibis 50% by weight ethylene, (B) 4 to 95% by weight of a styrene monomer or a mixture of a styrene monomer and one monomers copolymerizable therewith and (C) 4 to 95% by weight of a vinyl ester or a mixture of a vinyl ester and one copolymerizable therewith Monomers,