TW390898B - Composition for use in coatings and adhesives - Google Patents

Description

A7 ._B7__ 5. Description of the invention (1) The present invention relates to a composition suitable for papermaking, woodworking and related fields. This composition is particularly (but not exclusive) useful as an adhesive, a bonding agent, a coating, and a sealing material. There are a variety of adhesives available, especially for woodworking, containing polyvinyl alcohol (PVOH) or another polymer such as polyacetic acid Dispersion of vinyl ester < PVAc) in polyvinyl alcohol (PVOH). Adhesives work by forming physical bonds with the wood matrix. In this regard, the 0H group of the adhesive composition and the -0H group of the vitamine in the wood matrix together form a strong hydrogen bond. The problem with this type of adhesive is poor water resistance. As such, the use of such adhesives is limited. The unique water content of wood substrates can also cause difficulties with such adhesives. In addition, a variety of existing woodworking products use gold salts such as aluminum chloride and chromium nitrate for cross-linking or curing reactions (examples). The use of these metal salts is not good for the manufacturing and handling safety of adhesives. Alas, many current formulations containing low pH (about 3) may cause discoloration of tannin-containing wood. British patent GB 1423558 discloses a wood glue using a polyisofluoroester crosslinker. However, it is highly toxic and not suitable for environmental protection. Propidine has been used as a cross-linking agent for polymer injection molding compositions (GB 1424041) and for amine-containing synthetic material adhesives (JP 1026689). The present invention hopes to solve at least part of the aforementioned problems. In view of this, the present invention One aspect relates to a two-part combination package comprising components A and B, wherein component A contains Ai> a solution or dispersion containing a polymer containing hydroxyl units; and

Aii > — a polymer derived from the selective substitution of styrene monomer, the paper size is applicable to China National Standard (CNS) A4 (210X297 mm)

Hi vn a (Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs) < Μ-• n ^ mn ^ i ml ml m Neem A7 .B7 V. Description of the invention (2) Polymer, including carboxyl-containing units; and its component B includes:

Bi) A crosslinking hydrazone, including a multifunctional helium propidium, which can be crosslinked with at least one carboxyl group and at least one hydroxyl group. In this aspect of the present invention, the appropriate components A and B are liquid. In a preferred embodiment, the first openable container containing the components Ai> and Aii) and the second openable container containing the component Bi) are combined. In another aspect of the present invention, a composition is obtained by crosslinking the following components: Ai) —a polymer containing hydroxyl units and Aii> a polymer derived from a selectively substituted styrene monomer, the polymerization The product contains carboxyl-containing units, and Bi), a multifunctional aziridine cross-linking agent, which can cross-link with hydroxyl and carboxyl groups. In another aspect, the present invention is also directed to the use of a composition obtained by crosslinking the following components: AiV—a polymer containing hydroxyl units and AU) —a derivative derived from a selectively substituted styrene unit A polymer containing carboxyl-containing units and Bi), a multifunctional aziridine cross-linking agent, which is used as a protective coating, and is particularly used for derivatization of avidin or cellulose-containing products, including paper and Protective coating for wood products. Yet another aspect of the present invention is related to the use of the composition, which is obtained by cross-linking the following ingredients: Ai)-a polymer containing hydroxyl units and Aii)-a derivative derived from a selectively substituted styrene unit A polymer containing a carboxyl-containing unit, and Bi> a polyfunctional pyrrolidine cross-linking agent, which is used as a sticking agent, especially for wood products derived from streptavidin or wood containing vitamins and other Product adhesive. This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) II .-------- i I (Please read the precautions on the back before filling this page) Order 6-Central Standards Bureau of the Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 _ _B7_ V. Description of the invention (3) Other aspects of the present invention are the method of providing protective coating on wood and paper products and the method of sticking the surface of wood and paper products to other substrates. A preferred coating method comprises applying a composition of the invention in the form of a M spray. A method for properly adhering a substrate comprises applying a composition of the present invention to a substrate using a brush, a roller, or the like. In some preferred embodiments, the component Ai> is an aqueous polyvinyl alcohol solution. Polyvinyl alcohol can be selected from low and high molecular weight polymers. Also, polyvinyl alcohols having varying degrees of hydrolysis can be used. The appropriate choice of polyvinyl alcohol will depend on the desired characteristics of the composition, such as the desired viscosity. In another preferred embodiment, the component Ai) is an aqueous polymer dispersion which contains polyethylene as a stabilizer. Preferred polymers include acetate-containing units, which are commonly used in the woodworking sector, but many other polymers are also suitable. The polymer containing acetate units preferably comprises a polyvinyl acetate homopolymer or copolymer, and most preferably a polyvinyl alcohol-containing dispersion. Other examples of polymers as component Ai) include ethylene vinyl acetate copolymers and terpolymer dispersions. The preferred ingredient Ai) is water-miscible. It is also preferred that the polymer has a viscosity of about 20,000 to 80,000 mPas when measured at 23t !. Preferably, any such dispersion has a solids content of about 35% to 65%. Any such polymers containing acetate-containing units can be used alone or in combination. The preferred ingredient Ai0 includes a chemically modified styrene butadiene rubber latex. The preferred ingredient Aii) is water-miscible. The solid content of the preferred ingredients is from about 30% to about 70%. In addition to Ai) and Ai0, ingredient A may optionally include a filler material. Any filler material is required to improve water resistance. Qi filling examples include the paper size applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm) linn .--- 1 —-- (Please read the precautions on the back before filling in this page) Order --- --7-Printed A7 by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs _____ _ ^ _ B7_ V. Description of the invention (4) Talc, silica, kaolin or calcium sulfonate. One or more fillers are provided in the form of a fine powder or as a suspension in water. The amount of Qi filling can vary depending on the desired final properties of the composition. The filler prevents excessive penetration of the composition into the matrix. Fillers also provide better water resistance and film hardness to the final adhesive / coating. A suitable ingredient A contains no more than about 70% by weight of Qi filling. Preferred ingredient A contains up to about 50wU filler, preferably about 1% to about 50%, most preferably 30 to 45; ϋ. Ingredient A may also contain chemicals that are easy to store and handle, as is common in the industry. Ingredient A also contains other chemicals that improve the properties of the crosslinked film product. Optional additional chemicals / ingredients include thickeners (e.g. polyacrylic acid strips or avidin thickeners such as methyllevavidin or hydroxyethylstruvavidin), aromatic solvents and plasticizers (e.g. Dibutyl ester or benzyl phthalate) to improve the flexibility of the final polymer film. The components Ai) and Aii) can be used in various weight ratios, depending on the desired characteristics of the composition. Preferably, the ratio of Ai) to Aii > is in the range of about 1:10 to 10: 1. Optimal * Ingredient A contains approximately equal amounts of AU and Aii>. If the relative amount of Ai) is increased beyond this content, the water resistance and heat resistance of the resulting composition will decrease. On the other hand, if the content of component Aii) is increased, the adhesive strength of the resulting composition is reduced. In each aspect of the present invention, the polyfunctional cross-linking agent is one which can cross-link the hydroxyl group derived from the component Ai) and the carboxyl group derived from the component Aii). The cross-linking agent Bi) includes a polyfunctional aziridine cross-linking agent. Tejia gas propidine cross-linking agent is trifunctional, the best has the following formula This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm)

-8-V. Description of the invention (5)

Hr

WIRIN A7 B7

, CH-Y -N〆1

^ CH-Y

CH-Y wherein Y is a lower alkyl group containing 1 to about 4 sulfonium atoms. Preferably, γ is methyl. R is a polymer. A special multifunctional helium-propidine cross-linking agent (where Y is methyl) is available on the market. The cross-linking agent is named CAS No. 6426557-2. The proper added concentration of component B relative to component A does not exceed about 10 wt%, preferably about 1 to 5 wt% of component A, and most preferably about 3 wt% of component A. The best crosslinker is water-miscible. The aqueous dispersion of the crosslinker can be aided by a solvent such as methyl Glycol acetate and diol solvents are stabilized. This trifunctional aziridine crosslinker can crosslink components Ai) and Aii) and wood matrix as follows: Reacts with the carboxyl group of Aii > CH2-. CH-CH3. N | CH-CH3 0 R-Ν I II l ^ CH2 + 30H-C— ·. CH2 --- CH-CH3 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

ο 3-CH'C-H-hicih- nih- R

Reacts with the hydroxyl group of Ai) and the matrix (please read the precautions on the back before filling this page)

This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -9-V. Description of invention (6)

-CH] CH-CHj + 3 OH — R-N \ .CH2

N CH2-CH-CH, reaction direction H1CIH-Ν—Η

CH, C-H A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. Suitable aziridine crosslinkers can react with carboxyl groups at room temperature. As a result, the composition and the package of the present invention can produce a sticky effect or form a protective coating at room temperature. In a preferred embodiment of the present invention, the components Ai >, Aii) and B are appropriately selected to provide an adhesive or coating composition *, for example, which can be applied at room temperature without the need for additional catalysts as in conventional formulations. According to the present invention, the combination of components A and B is compared with the current product, and the former can provide a composition having improved adhesion and water resistance. The main preferred application of the present invention is the wood industry, such as wood bonding, which improves the corrosion resistance, chemical resistance and water resistance by adhering wood chips to form particle boards and wood coatings. However, the present invention can also be used in the paper industry, especially for coating paper to improve water resistance and rigidity. Can be used to produce cartons. In this regard * another aspect of the present invention relates to a particle board obtained by bonding wood chips with a composition including the components Ai), Aii) and Bi) as defined above. t is preferred, as the aziridine crosslinking agent as the component Bi), only f > H is about 10 to 11, particularly about 10.5. Typically the composition has an AUpH of about 4 to 5. The preferred ingredient Aii) is selected to have a pH of about 7.5 to 9.5. In this regard, including the ingredients AU, Aii) (Please read the notes on the back before writing this page in Thai) The size of the paper is applicable to China National Standard (CNS) A4 (210X 297 mm) -10-Central Ministry of Economic Affairs A7 __- _ ^ _ B7_ printed by the Bureau of Consumer Standards of the Bureau of Standards V. The composition of the invention description (7) and Bi) typically has a higher pH than the conventional technology composition pH-3. Specific examples of the present invention can provide compositions having a pH of about 6.5 to 8.5, particularly about 7-8. This has the advantage of reducing the possibility of discoloration of tannin-containing wood. Preferably, the ingredients Ai), Aii > and B are selected from adhesives that can provide an applicable period of 1-5 hours, preferably 3-4 hours. As mentioned above, the appropriate ingredients Ai), Aii > and BM enable water miscibility are selected. As such, the present invention also has the advantage of providing a cost-effective water-based system that is free of undesired solvents such as formaldehyde and phenol. In this respect * the present invention is superior to conventional techniques. Specific examples of the present invention will now be further illustrated with reference to the examples. EXAMPLES The formulation of the first example is as follows: Ingredients by weight

Ai > homopolymer polyvinyl acetate dispersion (PVOH > (solid content about 60¾) 30 pbw Aii > carboxylated styrene butadiene latex dispersion (solid content about 46-52%) 30 pbw Aiii) filler- Pasty (calcium sulfonate powder 60-70¾ in water) 40 pbw Preservative in the tank 0.5 pbw A combination contains two containers, one holding part A and the other holding part B. Part A is a blend of the aforementioned preferred ingredients Ai) to Aiii). Part B (crosslinking agent) is better than H3 Pbw's child added to the mixed dispersion before use (the size of the paper is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before (Fill in this page)

-11-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (8) A). In this example, B is a formula I in which Y is methyl. The properties of the formulation of the first example were determined and compared with commercially available adhesives. The test results are shown below. Test Results ® Sleeve; Li 1 Cross-linking agent Multifunctional hydrazine gold salt Catalyst adhesion effect Chemical bond Physical bond Reasonable water resistance Reasonable solvent resistance Reasonable poor Corrosion resistance Reasonable poor PH about 7-8, low discoloration effect about 3, High discoloration setting speed setting speed-easy to adjust medium-difficult to adjust aging time ¥ fast-less than 3 hours slow-at least 6 hours ¥ aging refers to the substrate after compression at room temperature until suitable for example by sawing wood or sanding Processing time. The proportion of the formula of Example I can also be changed depending on the desired end use and cost. However, the aforementioned formulations have been developed to provide the desired balance of final properties such as tackiness, cohesion and film hardness. It should be understood that the formulation of Example 1 contains equal amounts of ingredients Ai) and Aii). The following examples 2 and 3 illustrate the effect of changing the weight ratio of the two components on the final properties of the crosslinked product. Ingredients Ai), Aii > and Bi> same as above; only change its weight ratio 〇 The paper size applies the Chinese National Standard (CNS) M specification (210X297 mm) (please read the precautions on the back before filling in this congratulation) Φ. Order ----- -12-V. Description of the invention (9) Α7 Β7 Example 2 Ingredients by weight Ai) PVAc homopolymer (PVOH) dispersion 54 Ai i) XSBR 6 Ai ii) tincture paste 40 B : As in Example 1 Example 3 Ai) PVAc homopolymer (PVOH) dispersion 6 Ai i) XSBR 54 Aiii) Filler paste 40 B: As in Example 1 (Please read the precautions on the back before filling this page ) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to prepare a combined package containing a first container containing ingredients Ai) to Aiii) and a second container containing ingredient B alone. The formulation of Comparative Example 1 and the formulation of Example 2 have lower adhesive strength and lower water resistance and heat resistance. Comparing the formula of Example 1 again, the viscosity of the product of Example 3 is extremely low, so it is more difficult to apply it to a wood substrate. Depending on the nature of the wood matrix, it also results in varying degrees of cohesive strength. However, it does have good water resistance and heat resistance. The foregoing examples illustrate the effect of varying the content of each component in the combination package and composition of the present invention. Various modifications can be made to the foregoing examples. The size of the paper is applicable to China National Standard (CNS) A4 (210 × 297 mm) -13-

Claims (1)

590898 A8 B8 C8 D8 1. 2. 3. 4. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) No. 85106245. Qing Patent Scope Amendment Amendment Date: September 88-A combination package for coatings and desiccants, which contains: ~ 'Ingredient A contains one called a first polymer and a second polymer. Fate or point ", the second polymer of the township contains units with acetate; and-Α)) a third I house derived from a selective I-generation stupid ethylene single 1 '-epidemic direct polymerization The substance contains a unit with a gas base; the component B includes .................... Bin aziridine'-bite crosslinker "and at least one hydroxyl crosslink. Too: If the whole set of the scope of the patent application is inclusive, the first polymer is a homopolymer. D The combination package according to item 1 of the scope of patent application, wherein Ai) comprises a solution of polyvinyl alcohol in which r is a double first polymer. For example, the application package of item 1 of the scope of patents, where 4i) contains-eight_ powder, the dispersion liquid contains polyvinyl alcohol as the first polymer 7 '. (Ai) is a polyacetate, homo-, poly-, or co-. Poly. .... such as the combined package of item 5 of the scope of patent application, where Ai) is a dispersion containing vinyl acetate and homopolymer. For example, the combination of item No. 4 in the scope of patent application: package-people-of which, Ai) contains-Jiwei Tongnong Chelu Copolymer or Tripolymer. -14 · (Please read the precautions on the back before (Fill in this page) 590898 A8 B8 C8 D8 1. 2. 3. 4. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) No. 85106245. Qing Patent Scope Amendment Amendment Date: September 88-A combination package for coatings and desiccants, which contains: ~ 'Ingredient A contains one called a first polymer and a second polymer. Fate or point ", the second polymer of the township contains units with acetate; and-Α)) a third I house derived from a selective I-generation stupid ethylene single 1 '-epidemic direct polymerization The substance contains a unit with a gas base; the component B includes .................... Bin aziridine'-bite crosslinker "and at least one hydroxyl crosslink. Too: If the whole set of the scope of the patent application is inclusive, the first polymer is a homopolymer. D The combination package according to item 1 of the scope of patent application, wherein Ai) comprises a solution of polyvinyl alcohol in which r is a double first polymer. For example, the application package of item 1 of the scope of patents, where 4i) contains-eight_ powder, the dispersion liquid contains polyvinyl alcohol as the first polymer 7 '. (Ai) is a polyacetate, homo-, poly-, or co-. Poly. .... such as the combined package of item 5 of the scope of patent application, where Ai) is a dispersion containing vinyl acetate and homopolymer. For example, the combination of item No. 4 in the scope of patent application: package-people-of which, Ai) contains-Jiwei Tongnong Chelu Copolymer or Tripolymer. -14 · (Please read the precautions on the back before (Fill in this page) 8 8 88 ABCD SSQ898 Scope of patent application 8 · ★ Patent application JH X sensitive package, where A ii) includes a carboxylated, naphthalene vinyl butadiene rubber latex. 9, such as the application package of the scope of the first patent package, where the component A contains heavy ......... — "Ai) and Aii) in the amount ratio between 1:10 to 10: i. 10. For example, the combination package for item 9 in the scope of patent application, where component A contains a weight% between 1: 5 and 5: 1; Ai) and Aii). 11. For combination package in the scope of item 1, where Ingredient 4 contains Δί) and Aii) of about 1: 1 electricity consumption per night. '12. If the combination package of the scope of application for item 1 is ..., which contains ingredient A in addition, there is Aiii) —or more than one. Filling agent, and / or ... eight or one or more. Preservatives. 13. If the combination of the scope of the application for the first item of the package, where the component B includes Bi). .Crosslinking agent CH2-/ HY 1 I > / Yan Y?-\ 1 / N \ CH2 CH2-CH-Y Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R is a polymer chain and Y is A low-carbon alkyl group containing 1 to 4 carbon atoms. 14. For example, the package of item 13 in the scope of patent application, wherein Bi) is a trifunctional aziridine crosslinking agent, wherein γ is methyl. 15 · If you apply for a combination package of item 1 of the patent scope, the Water-soluble L .. V -..........-', mixed. 16. ·.' If the package of the scope of application for item i of the patent package, where Ai) and Aii) are the paper standard Applicable to China National Standard (CNS) A4 specification (210X297 mm)-A8 Water miscible. 17 • If the combination package of item 1 of the scope of patent application, components A and B are provided in a weight ratio of 100 to 10 to 100 to 0.1. 8 · If you apply for the combination package of item 17 in the scope of the patent application, the weight ratio \ ............... iOO to 5 and 100 to 0.1 of the components A and B. 19 · The combination package according to item 1 of the scope of patent application, in which component A is additionally packaged-containing a variety of _ fillers selected from the group consisting of calcium carbonate, talc, silica and kaolin. 2〇υ · composition, which can be obtained by cross-linking the components Ai) and Aii) with B),. Ai)-a solution or dispersion comprising a first polymer and a second polymer, The first polymer contains a monofluorene having a hydroxyl group, and the second polymer contains a unit having a root; and 'Aii) — a third polymer that is multiply derived from a selectively substituted styrene, and a third polymer Units that include _carboxy-groups; ra).-More than one official ~ energy aziridine. 唆 cross-linking agent '~ which can be combined with at least _ slow and a at least _ hydroxyl m 〇 21. 7 kinds will be a first Cellulose matrix is adhered to an article of two-dimensional formula .............. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The method includes combining a component A And component B, from the provision of a dry, admixture; component A cover contains Ai) — including a first polymer and a second polymer .. .. .. solution or dispersion, the first polymer The compound contains a unit with a base, the second polymer contains a unit with an acetate; and; Aii)-a third aggregate derived from a selectively substituted early styrene precursor, the third Carboxyl group Units: • 16- This paper size applies Chinese National Standard (CNS) A4 specifications (210χ; 297 public holidays) stasis B8 D8 6. The scope of patent application includes households with Bi) —multi-i-nitrogen two hydrazone crosslinkers, which It can be: that at least one carboxyl group is crosslinked with at least one hydroxyl group; and then: the adhesive is applied to the __ area of the __ fiber male substrate, and the second substrate and the policy A cellulose matrix talks about the first area. 22. ^ A method for protecting a cellulose matrix, which comprises a combination of—component a and, two components B, ′-…… 成. 分 ^ 包 —including Ai) — including a first polymer and ~ ^. 第. 二Polymer.soluble-liquid-or-dispersed, the first: _ polymer contains ... with a poly group, the unit, the second polymer. The substance contains a unit with ethyl acetate; and a Yan. ▲ Zhenyi's selective accumulation of the article 'Third Couplings of Dilute Monomers < Objects' This third polymer contains units with a carboxyl group; 〃 Component B includes Bi) — polyfunctional. A pyrimidine cross-linking agent, which can be cross-linked with at least two amines and one major hydroxyl group; then, the resulting combination is applied to the substrate. 2 3 _ Yili particle board, which includes wood chips that are stuck together with a composition, the composition contains, a mixture of a component A and a component B, the component A includes Ai) — \ includes a A solution of a first polymer and a second polymer, the first polymer containing and having a unit with a warp group, the second polymer containing a unit with an acetate group; and Aii) —derivative From a third polymer that selectively replaces styrene monofluorene, the third polymer includes units with several fluorene; Component B includes Bi) —multi-functional, energy-containing nitrogen. Propidine cross-linking agent ___ -17-. • — ^ 1 nn ^^^ 1 n ^ in I— ^ I n (Please read the notes on the back before filling out this page) Order printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs · This paper Standards are applicable to Chinese National Standards (CNs) A4 regulations (2. 0x297 mm) 390 Look | D8, patent application scope 丨 less one carboxyl group at least one hydroxyl cross-linking. 24 · —A kind of wood product, which includes a two-component wood substrate which is glued together. The composition package contains a mixture of component A and component B, and the components include: Ai) — including — including. A first polymer and a second polymer ~ multi-liquid. Or dispersion "" The first polymer contains a unit with a scientific base: the A polymer contains a unit with an ethyl-acid radical; and jii ) A third polymer derived from a selectively substituted stupid ethylene monomer. The third polymer includes a unit having a carboxyl group; $ 分 B includes Bi) — a polyfunctional nitrogen-propidine crosslinker, which It can be crosslinked with at least one carboxyl group and at least one trace group. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs! Zhang-Paper / V Standard Standard Country I China I 用 Thin Public 7 9 2 (Please read the precautions on the back before filling this page)