TWI251609B - Ethylene copolymer pellets - Google Patents

Abstract

Ethylene copolymer pellets having improved unsusceptibility to blocking are provided. The ethylene copolymer pellets comprising a mixture of: (a) 100 parts by weight of an ethylene copolymer; (b) 0.01-0.5 part by weight of an unsaturated fatty acid bisamide having a melting point of 100-180 DEG C; and (c) 0.01-0.5 part by weight of a lubricant having a melting point of 60-90 DEG C, which, when used in combination with ingredient (b), lowers the melting point of ingredient (b) by at least 20 DEG C.

Description

1251609" Case No. 931 ribs 7 V. OBJECT DESCRIPTION OF THE INVENTION (1) Technical Field of the Invention The present invention relates to an ethylene copolymer colloid, and more particularly to an ethylene copolymer colloid for colloidal particles. Melting bonds (fusi〇nb〇ndlng) (hereinafter referred to as pellet blocking) have improved unsusceptibility. [Prior Art] Due to ethylene copolymer colloids such as ethylene/vinyl acetate (ethylene/vinyl acetate) copolymer (hereinafter referred to as EVA) has very good tackiness, so it will cause very serious agglomeration of each other during the manufacture or subsequent storage and transportation of the rubber particles (b 1 Ock ) 'In addition, another problem with rubber pellets is that due to the very low flow rate (f lowabi 1 ity ), more labor is required in the manufacture and packaging of the rubber pellets, and storage and transportation are carried out for a long time. There are also many difficulties encountered. In order to reduce these problems, many methods for processing colloidal particles have been proposed so far. Technical packages for preventing colloidal agglomeration (pe 1 1 etb 1 〇cking) Included: coating the surface of the colloidal particles with inorganic substances such as talc (ta 1 c ), si 1 i ca , fine polyolefin (po 1 y ο 1 efi η ) particles, polyethylene fibers or the above Dispersion type of matter (dispersi ο η ); in addition, the colloidal particles can also be mixed with higher fatty acids or their salts, such as N, N' - ethylene diterpenoid (N, N'_ethylenebis 〇leamide ), N,N'-ethylene N-N-ethylenebiserucamide, (N,N,-dioleyladipimide) (Ν,Ν'-dierucyladipimide), but these methods still have many problems.

7042-6149-PFl(N2).ptc Page 6 1251609 _ Case No. 931Q32Q7 Year Month Revision 5, Invention Description (2) For example, 'adding inorganic substances such as talc (talc) or sillca and EVA In the case of mixing and adhering to EVA, it is necessary to add a large amount of inorganic substances to obtain better colloidal flow force (f 1 〇wabty )', but the use of a large amount of inorganic substances may lower the function of the final product because of inorganic substances. The compatibility with EVAs is very poor. The aqueous slurry (aqUeous siurry) coated with fine polyolefin (p 〇1 y 〇1 θ f丨η) particles of the χ κ κ knee has a problem due to the fine poly olefin particles in the aqueous phase system. The dispersion in the dispersion is very poor' and it is not easy to adhere to the rubber particles, so this technique can not reduce the tackiness to a certain degree to obtain a satisfactory flowability (see, for example, the United States). Patent No. 3,528,841). In the case where the EVA colloidal particles are coated with polyethylene, disperse (diSpersi〇n) or polyethylene wax as a main component, the tackiness of the colloidal particles can be effectively reduced to To a certain extent, however, effective flow force (n〇wabiHty) cannot be obtained, and there is another problem with this method, that is, when the coated colloidal particles are melted and appear milky white, the coating obtained by using this technique is coated. The application of the rubberized granules will be limited (see, for example, Japanese Patent No. JP~A~5 6-6 72 〇9). Furthermore, in the case of the low-adhesive EVA dispersion of the colloidal particles of the gum adhesive ethylene polymer, the reduction in tackiness and the satisfactory flow force (ilowability) are still not obtained. ), because EVa used as a coating material has a low melting point, although this melting point depends on the vinyl acetate in the coating material.

7042-6149-PFl(N2).ptc Page 1251609 V. Description of invention Case No. (3) 93103297 Year of the month _ The amount (see Japanese Patent No. jp-A-48-320 39). A method of mixing a higher molecular weight fatty acid or a salt thereof (see, for example, JP-A-5 6- 1 3 6 34 7) or adding the following N,N,-ethylene bis-indoleamine (N, N) , -ethylenebisoleamide ), N, N' - Ethylene bismuth sulphate (Ν, Ν ' -ethylenebiserucamide ), (N, N'-di〇leyladipimide), (Ν, Ν ' - dierucy ladipimide ) group of compositions The method (see Japanese Patent No. JP-A-5 7-2 0 043 4) has been suggested to be used 'but these methods have the following disadvantages: because the rate of bleeding of these additives is not fast enough, The initial prevention of colloidal blocking is poor. SUMMARY OF THE INVENTION In view of the above, it is an object of the present invention to provide an ethylene copolymer colloid having improved unsusceptibility to colloidal agglomeration (b 1 〇ck i ng ). The inventors of the present invention have made intensive studies on the above problems, and they have found that the addition of a specific lubricant to the ethylene copolymer can reduce the phenomenon of blocking of the ethylene copolymer micelles, and the present invention It is based on this discovery. In order to achieve the above object, the present invention comprises a batch of ethylene copolymer colloidal particles, including a mixture: (a) 1 part by weight of an ethylene copolymer·Q b) 〇·〇1~〇. 5 parts by weight of -(bisamide) has a melting point of 1 〇〇~180 π both you and the fatty acid;

1251609 ^S 93103297 曰Revision 5, invention description (4) (c) 0 · 0 1~〇· 5 parts by weight of a lubricant (1 ubricant) has a melting point of 60 0 to 90 ° C when used in When combined with the component (b), the melting point of the component (b) can be lowered by at least 20 °C. [Embodiment] The present invention will be described in more detail as follows: The ethylene copolymer (a) used in the present invention is not particularly limited, and the polymer of the ethylene copolymer referred to in the examples includes ethylene/α, /3 - Unsaturated carboxyl ic vinegar copolymer, ethylene/vinyl ester copolymer, ethylene/vinyl ester / 〇:, /3 - unsaturated carboxylic acid terpolymers and ethylene / α-olefin copolymer, and ethylene copolymer Specific examples include ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/1-butene copolymer, ethylene/ 1-hexene copolymer, ethylene/1-octene copolymer, ethylene/4-methyl-1-pentene copolymer, ethylene/propylene copolymer rubber, ethylene/propylene/diene copolymer rubber and ethylene/butyl An olefin copolymer rubber in which an ethylene/ethyl acrylate copolymer having a low softening point is preferably used. The above ethylene copolymer (a) is more preferably an ethylene/vinyl acetate copolymer having an ethylene/vinyl acetate copolymer having a vinyl acetate content of 27 to 5 wt% according to the identification of JIS K6924-1 (1999). Acetate content (abbreviated as VAc), and according to the measurement of JIS K6 924-1 (1 9 9 7 ), the melt flow rate (MFR) of the acetonitrile/vinyl acetate copolymer satisfies the following relationship: 0. 7731 MFR > 43 1. 98 x ( VAc

7042-6149-PFl(N2).ptc Page 9 1251609 Case No. 93103297 One year 曰 Amendment 5, invention description (5) Therefore, the ethylene/acetic acid ethylene vinegar copolymer preferably has a tendency to agglomerate. (ie has high VAc and high MFR). The unsaturated lipopeptide used in the present invention is a bisamide (b) having a melting point of 1,0 0 to 180 ° C, such as 士 _ _ μ Such as the extended fatty acid bismuimide (b) includes: ethylenebisstearamide, ethylenebisoleamide, r κ 々 ethylene bismuth oxime (ethyleneblserucamide) and ethylene double Laurel amine (ethyleneblSlaUr(10)1de), of course, from the viewpoint of the phase and bleeding properties of the ethylene copolymer, B = (ethylenebisoleamide) is preferred. Also, the private ethylene polymer (a) is 1GG. The amount of the acid acid amine (Hsamide) (b) used in the case of parts by weight is 〇.〇1~/fat, and preferably 0.05 to 0.2 parts by weight. μ 4 · a bis (bisanude) (b) When the amount is less than 〇.〇1 parts by weight, the effect of the gel = amine block is low; in addition, if the amount of the unsaturated fatty acid bis-amine (bis " ·, anti-knot (b) is more than 0.5 parts by weight, the longer the time , no more = = de) bisamide (b) The greater the amount of flow to the surface, this will 曰 ~ fatty acid double More serious, such as a decrease in adhesion. "The problem of the lubricant (lubricant) (c) used in the present invention is limited, but there is a melting point of 60 to 90 Ό, so that it does not have When the specific fatty acid diamine (bis am i de ) (b) is combined, the unselfishness, the residue and the fat can be reduced -..... ^ ^ $bi sami de (b) The melting point is at least 20 ° C. This lubri cant ) (c) includes the monthly fatty acid and the monthly fatty acid ammonia.

闰闰滑齐lj

7042-6149-PFl(N2).ptc Page 101251609 Case No. 93103297 Yearly Revision 5, Invention Description (6) (lubricant) (c) When the melting point is less than 60 °C, the anti-caking of the rubber particles ( Μ 〇cking ) has a small effect; in addition, if the melting point of the lubricant (1 ubricant ) ( c ) is greater than 90 ° C, the initial anti-caking effect of the colloidal particles is poor. Specific examples of lubricants (c) include saturated fatty acids such as stearic acid, hexadecanoic acid or behenic acid' with unsaturated fatty acid ammonia such as erucamide or oil oxime. Amines (ο 1 eamide ), these compounds may be used singly or in the form of a mixture thereof. Among these lubricants, unsaturated fatty acid ammonia which can be quickly moved to the surface and has a good anti-caking effect is preferably used, and better use can improve the bisamide (b) bleeding phenomenon of the unsaturated fatty acid. Mustard erucamide. In the case where the ethylene polymer (a) is 100 parts by weight, the lubricant (c) is used in an amount of 0.01 to 0.5 parts by weight, and preferably 0. 0 5 to 0 · 2 parts by weight. . If the amount of the lubricant (1 ubricant ) (c) is less than 0 · 0 1 part by weight, the anti-caking effect of the rubber particles is low; in addition, if the amount of the lubricant (c) is more than 0.5 parts by weight The longer the time, the greater the amount of lubricant (c) flowing to the surface, which can make the problem worse, such as reduced adhesion. The weight ratio (b)/(c) of the unsaturated fatty acid bisamide (b) to the lubricant (lubricant) (c) is preferably 70/30 to 3 0/70, and the terminal is unsaturated. The bleating of the fatty acid bisamide (b). The method of adding a lubricant (c) to the present invention is not limited, and any method which can be used can be used to obtain the colloidal particles, such as these.

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Page 11 Case No. 93103297 Year 1251609

V. INSTRUCTIONS (7) The method comprises: treating with an extruder (Miller mlEer), a kneading machine Uneader, etc. (Banbury kneading Uelt-kneaded); or applying a softening agent to these components The surface of the colloidal particles; or dry-blended with the lubricant and the gel. In the above method, the mixture of V and L forms from the melt-kneading to obtain the square of the colloidal particles θ 70,000 is preferable because it has an improved unsusceptibility for the agglomerate (blockmg ) (unsusceptibility) ). 曰

The ethylene copolymer colloid of the present invention is measured according to the JIS surface 1 (1 994), and has the opposite surface; the chain ^ is 1V effect, the flow knife v fiowabi ii ty ) and +, p 仏士 I 丄7 to s, Ra is preferably l 〇~2, 5 ,. In the present invention, there are many surfaces for the colloidal particles.

Use, for example, cutting, such as water cutting, wire cutting Hungarian IJ ', urinary enthalpy or hot cutting, these methods are to make the rubber particles through a groove with a lattice pattern (n wood y彳, nur 1 ing) A protruding transmission line or a transfer line having a concave and protruding shape having an echo pattern in a ring shape. The surface roughness Ra of the present invention was measured using a laser microscope νκ_δ5〇〇 (manufactured by Keyence). The ethylene copolymer colloid of the present invention may include pigments, dyes, antioxidants, lubricants, weathering agents, anti-caking agents, various stabilizers, inorganic fillers, and the like, as needed. The invention will be explained in more detail by way of the following examples and comparative examples, but the invention is not limited by these examples. In the following examples and comparative examples, the following test methods were used.

121251609

For the evaluation of the effectiveness: the gelatinous agglomeration (b ◦ 1 cking) test of the rare-community box 6 8.8 24 small amount of B is now processed by kneading (meU-kneadlng) treatment of 1 (10) grams of B K > The pellets were placed in a test piece of test size Plece pr〇ductl〇nb〇x ) with an internal dimension of 60 X 60 0 60 mm, on which the force of the load was applied and maintained at 30 C for 48 hours, followed by Maintaining % at 23, the resulting test piece was compressed at a rate of 1 〇mm/min to measure the maximum load required for damage; further, it was placed at 23 and the next time the olefin copolymer was also taken. Do the same test. If the test piece has a caking force of less than 490 N, it is rated as "good". If it is cut N or higher and 5 is "poor", these test results are listed in Table 2. Test for the drop of the melting point of the mouth (2) for the unsaturated fatty acid blsamide ((9) for the shame curve, the peak at the highest melting point of the curve is called Tm 1 ; for the unsaturated fatty acid biguanide ( Bisamide ) (b) with the lubricant (1 ubr i can t ) (c) for the DSC curve of the formula 3 'the peak at the southernmost melting point of the curve is called T m 2 ; and T m 1 and T m 2 The difference is the decline of the melting point. These test results are listed in Table 2. α Example 1 According to the plan shown in Table 1, it will have an MFR of 40 0 g/l〇min and a VAc amount of 33% ( Ultrathene (Nip〇f 1 ex ) 0B54B, by

100 parts by weight of ethylene/ethyl acetate copolymer manufactured by Tosoh Corp. and 0.1 part by weight of ethylenebis〇leamide and 0.1 part by weight of erucamide Kneading

7042-6149-PFl(N2).ptc Page 13 1251609 93103297_年月—曰佟丨下_五、发明说明(9) (melt-kneaded), and then the resulting mixture is then subjected to water cutting. The surface is thickly chained 'so' to obtain a rubber particle with a surface roughness of 1 · 6 // m, and the obtained rubber particles are used for identification of b结ock i ng strength, The melting point Tml of ethylenebisoleamide is 120 ° C, and the melting point of erncamide is 8 (rc, 5 〇 5 〇 (纣%) ethylenebisoleamide spinning? Father Captain.../ · ι x amiue er 介 介 ( (erucami (je) melting point Tm2 is 75 t: 'The measurement of these melting points and the blocking strength are measured in Table 2 .

1251609 Case No. 93103297 曰Revision 5, Invention Description (10) Comparative Example 4 Comparative Example 3 Comparative Example 2 Comparative Example 1 Real 臓 4 1 Example 3 Bao Shi Example 2 Bao Shi Example 1 EVA EVA EVA EVA EVA EYA EVA 1_ SK ittnp 台-〇g 400 4^ 〇台〇台〇4^ g 〇MFR (g/10min) UO Lk) oo 〇〇υο U0 〇〇υο UO 〇〇υο Lk) comonomer content (Wt °/o) Ethylene bisinamide 1 Ethylene bisamine amide! Ethylene bisamine phthalate ethylene bisamine phthalate 1 ethylene bisamine phthalate acesulfame 双 I ^ II Οι~~1 iwh 1 δ 1 〇0.05 S CD (parts by weight) mustard toluidine mustard amide 1 1 chloramine glucosamine mustard amide amine mustard amide lubricant 0.05 1 1 〇0.05 S 9 liters (parts by weight) softening kneading softening 揉Pinch softening kneading 1 softening kneading softening kneading softening kneading softening kneading addition method S: surface roughness (μηι)

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I 1251609 Case No. 93103297 曰 V. Description of invention (11) Revision Table 2

Tml Tm2 melting point drop binding force [N] rc) ra rc] Immediately after one month Example 1 120 75 206 洼1S6 Good Example 2 120 75 45 78 Good 59 沣 Example 3 120 75 45 441 Good 392 Good Bao Shi Example 4 120 SS 35 Biega 27A Good Comparative Example 1 - A M90 Difference > 490 Difference Comparison Example 2 - One & One 490 Difference 314 Good Comparison Example 3 - - One > 490 Difference > 490 Difference Comparative Example 4 120 103 17 > A9Q Difference 190 沣 Example 2 Will have an MFR of 40 0 g/l〇min and a vAc amount of 33% (Ultrathene (Nipoflex) 0B54B, manufactured by Dingoso Corp.) 100 parts by weight of the ethylene/vinyl acetate copolymer with (K 5 parts by weight of ethylenebisoleamide and 0.5 part by weight of erucamide) softened and kneaded (meit-kneaded) Then, the obtained mixture is further subjected to water cutting to roughen the surface of the rubber particles. Therefore, a rubber particle having a surface roughness Ra of 1.6/m is obtained, and the obtained rubber particles are taken as a knot. Identification of the block force (b 1 〇ck i ng s ΐ r eng 1:h ), these measurements are Table 2 Example 3 having an MFR of 40 0 g / 10 min and an amount of 33% VAc

7042-6149-PFl(N2).ptc Page 16 1251609 Case No. 93103297 V. Description of invention (12) (UUrathene (N 丄P〇f 1 ex ) 〇B 5 4 B, by T〇s〇hc〇rp. Manufactured) 100 parts of the ethylene/vinyl acetate copolymer and 〇. 〇 5 parts by weight of ethylenebisoleamide and 0.05 parts by weight of erncamide (meH — kneaded ) 'The mixture obtained is then subjected to water cutting to coarsely saccharify the surface of the colloidal particles. Thus, a colloidal particle having a surface roughness Ra of 丨·6 # m is obtained, and the obtained colloidal particles are taken. For the identification of b 1 〇cking strength, these measurements are shown in Table 2. Example 4 100 parts by weight of an ethylene/ethyl acetate copolymer having an MFR of 40 0 g/l〇min and a VAc amount of 33% (Ultrathene (Nipof1 ex ) 0B54B, manufactured by Tosoh Corp.) 5 parts by weight of ethylenebisoleamide and 0.05 parts by weight of oleamide are melt-kneaded, and then the resulting mixture is further subjected to water cutting to make a gel. The surface of the granules is roughened, so that the colloidal particles having a surface roughness Ra of 1.6 · m are obtained, and the obtained colloidal particles are used for the identification of the caking force (b 1 〇 ckings ΐ rength). The measurement of the melting point drop and the binding force (b 1 ockingstrength) of a mixture of 0.1 parts by weight of ethylenebisoleamide and 0.1 part by weight of oleic acid amine (ο 1 eamide ) are listed in the list. 2 in. Comparative Example 1

7042-6149 Marriage (N2) ptc Page 17 1251609 Case No. 93103297 Year Month_Day Revision V, Invention Description (13) Will have an MFR of 40 0 g/l〇min and a VAc amount of 33% (Ultrathene (Nipoflex) 0B54B The surface of the rubber particle of the ethylene/vinyl acetate copolymer manufactured by Tosoh Corp. is roughened, and thus, a rubber particle having a surface roughness Ra of 1.6 K is obtained, and the obtained rubber particle is obtained. Used for identification of the caking force (Μ 〇ckingstrength), these measurements are shown in Table 2. These micelles are useless because of their high blocking strength. Comparative Example 2 100 parts by weight of an ethylene/vinyl acetate copolymer having an MFR of 40 0 g/10 min and a VAc amount of 33% (Uitrathene (Nipoflex) 0B54B, manufactured by Tosoh Corp.) was used. 0 · 2 parts by weight of ethylenebisoleamide - softened and kneaded (me 1 ΐ - kneaded ), and then the resulting mixture is further subjected to water cutting to roughen the surface of the rubber particles, thereby obtaining The rubber particles with a surface roughness Ra of 1.6 /zm were used for the identification of the caking force (b 1 〇ckingstreng ΐ h ). These measurements are shown in Table 2. Since these colloidal particles have a high degree of blocking strength just after production, the households are useless. Comparative Example 3 will have an MFR of 40 0 g/10 min and a VAc amount of 33% (Uitrathene ( Nipoflex) 0B54B, made by Tosoh Corp., manufactured by Tosoh Corp., 100 parts by weight of ethylene/vinyl acetate copolymer and 0.2 parts by weight

1251609 Case No. 93103297 Earth Moon Correction V, erncamide of the invention (14) - softening kneading (meH - kneaded )' and then the resulting mixture is further subjected to water cutting to roughen the surface of the rubber particles, thus The micelles having a surface roughness Ra of 丨·6 V m were obtained, and the obtained micelles were used for the identification of blocking strength'. These measurements are shown in Table 2. Because these colloidal particles have a degree of blocking strength after they are produced, they are useless. Comparative Example 4 100 parts by weight of ethylene/vinyl acetate copolymerized with MFR of 400 g/l〇min and vac amount of 33% (Ui trathene (Ni ροΠ ex ) 0B54B, manufactured by Tosoh Corp.) And 〇. 1 5 parts by weight of ethylenebisoleamide and 0.05 parts by weight of meson S&fec (erucamide) together with soft kneading kneaded), and then the resulting mixture is further subjected to water cutting to make the rubber particles The roughening of the surface 'so' gives the colloidal particles with a surface roughness ra of 1 · 6 # m, and the rubber particles that are applied are used for the identification of the caking force (b 1 〇ckingstrength ). The measurement of the melting point drop and the blocking strength of a mixture of 15 parts by weight of ethyl enebi sol earn ide and 5 parts by weight of erucamide The measurements are in Listing 2. These pellets are useless because they have a high degree of blocking strength just after they are produced. As described above, the ethylene copolymer colloid of the present invention can improve the block resistance

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7042-6149-PFl(N2).ptc Page 20 1251609 Case No. 93103297 Revised

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Claims (1)

Msmmi Case No. 93103297 9 Year of the Month, 曰6, Patent Application 1 · An ethylene copolymer colloid, including a mixture: (a) 100 parts by weight of an ethylene copolymer; (b) 0.01~ 0.5 parts by weight of a non-saturated fatty acid bisamide having a melting point of [8〇 °c; and (c) 0·0 1~0. 5 parts by weight of a lubricant (lubricant) It has a melting point of 60 to 90 ° C. When used in combination with component (b), the melting point of component (b) can be lowered by at least 20 °C. 2. The ethylene copolymer colloid as described in claim 1, wherein the mixture is obtained by a soft kneading treatment. 3. The ethylene copolymer colloid as described in claim 1 or 2, wherein the ethylene copolymer is an ethylene/vinyl acetate copolymer. 4. The ethylene copolymer colloid as described in claim 1 or 2, wherein the ethylene copolymer is an ethylene/vinyl acetate copolymer comprising a vinyl acetate, and the content of the vinyl acetate (VAc) According to JIS K6924- 1 (1 9 97), the identification result is 27 to 50% by weight and its melting flow rate (MFR) satisfies the following relationship according to JIS K6924- 1 (1 997): MFR > 431. 98x ( VAc) ~0·7731 〇5. The ethylene co-tomer colloid as described in claim 1 or 2, wherein the unsaturated fatty acid bis amide (b) and the lubricant ( 1 ub ric an t ) (c ) The weight ratio is 7 0 / 3 〇~3 0 / 7 0 ° 6 · The ethylene co-support as described in item 1 or 2 of the patent application 7042-6149-PFl(N2).ptc Page 22 1251609 Case No. 93103297 Amendment 六6, the patentable range of rubber particles, wherein the unsaturated fatty acid double amine (bis am i de ) (b) is ethylene double oil (et hy 1 eneb i so 1 earn ide ) o 7. The ethylene copolymer colloid as described in claim 1 or 2, wherein the lubricant (c) is an unsaturated fatty acid amine. 8. The ethylene copolymer colloidal particle of claim 7, wherein the unsaturated fatty acid amine is erucamide. 9. The ethylene copolymer colloid as described in claim 1 or 2 has a surface roughness which is 1 according to JISB 0 6 0 1 (1 9 9 4 ). 0~2. 5 // m. 7042-6149-PFl(N2).ptc Page 23