Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J191/00—Adhesives based on oils, fats or waxes; Adhesives based on derivatives thereof
  • C09J191/06—Waxes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
  • C08L91/06—Waxes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/04—Homopolymers or copolymers of ethene
  • C09J123/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
  • C09J193/04—Rosin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00

Definitions

• the present invention relates to a hot melt adhesive composition. Further,
• the present invention relates to a novel hot-melt adhesive composition containing a specific stabilized ⁇ £ -based resin as a tackifying resin and having excellent heat resistance and wettability.
• Hot melt adhesives are solid at room temperature, are heated and melted at the time of use, applied to various substrates, adhered, cooled, and solidified to develop adhesive strength. It is something to be done.
• the hot-melt adhesive has a solid content of 100%], which reduces the risk of fire and reduces the bonding time by 5 times. It has many advantages, such as easy handling, and has been awarded in various fields, such as bookbinding, packaging, and woodworking, with the rapid spread of the alicator.
• Such hot-melt adhesives are usually used as a base polymer such as an ethylene-vinyl acetate copolymer or an ethylene acrylate copolymer.
• Ethylene-based base polymer such as an ethylene-vinyl acetate copolymer or an ethylene acrylate copolymer.
• OMPI Polymer Polyethylene, Thermoplastic: Thermoplastic, Polyad, Polyurethane, Polyester, and other thermoplastic polymer materials are used to provide adhesion. It is composed of a resin and various waxes as a viscosity modifier. The rims of the above-mentioned pas-ports include flexibility, heating stability, price, etc.] 4) Etch such as ethylene acrylate Copolymers are widely used.
• tackifying resin natural resins such as ⁇ 5 pen or various petroleum resins are used.
• Terpene 2 / resin which is mainly made of Terpene's phenolic resin, has excellent heat stability and pet timing, but it has excellent properties. Not satisfactory in terms of heat resistance, cold resistance and odor. 5
• Various types of petroleum resins obtained by polymerizing a more inexpensive petroleum fraction as a raw material have been proposed as a tackifying resin that can be used as a replacement for 05-based or terpene-based resins. Although it has relatively good settability, its properties such as compatibility, heating stability, adhesion, and cold resistance are still not comparable to the above-mentioned lO natural resin.
• any of the conventionally known tackifying resins can be used in at least one of the following properties: heat stability, compatibility, adhesiveness, wet time, and cold resistance. Inferior! ) However, no satisfactory hot-melt adhesive has yet been obtained.
• the present inventors have to develop a novel useful hot-melt adhesive in which the above-mentioned drawbacks have been improved, and have developed a stabilizing port having relatively excellent properties even among conventionally known tackifying resins. With a focus on the 5th esteem, they worked diligently. As a result, when a specific stabilized resin is used as the tackifying resin, all of the above-mentioned disadvantages can be solved at the same time.
• the present invention provides a hot-melt adhesive composition containing a copolymer / wax and a tackifier resin as main components, wherein the tackifier resin is partially The disproportionation port X stayed in a marled and Z or partially maleed state (hereinafter referred to simply as a “stabilized lone resin” lo)
• the present invention relates to a melt adhesive composition.
• composition of the present invention provides the basic performance required for a hot melt adhesive composition, that is,
• heat resistance adhesiveness at high temperatures
• the composition of the present invention has recently been widely used in packaging, assembling (assembly), etc. 5)
• heat resistance and set time are particularly desirable. As can be seen, it is very effective in conformity with the current situation where the development of hot-melt adhesives having such excellent properties is highly desired.
• the stabilizing port 5 ⁇ ZIlO-based resin used as a tackifier resin in the composition of the present invention has higher heating stability, settability, etc. as compared with conventionally known ordinary b-based resins. It is excellent in terms of heat resistance, 5) and, in comparison with Terpen-F-I-Nole resin, it is particularly excellent in heat resistance, cold resistance, odor and the like. Conventionally, a tackifier resin having such various properties has not been developed.
• the quinone-based resin is a disproportionated ester with partial fumigation and no or partial male 1 /.
• a resin can be produced according to a known method. As an example of the method, a partial malformed mouth 05 and / or a partial male! Reaction of 52 / with alcohol to produce lone esdell and disproportionate
• a trivalent or higher-valent alcohol is preferred.
• the multivalent alcohol include ⁇ resellin, ⁇ resellin, pentaerythritol, and ⁇ petalysitol.
• a five-step reel is preferably illustrated.
• the above-mentioned esdelation reaction can be carried out in the same manner as in a usual esdelation reaction method. That is, for example, both components can be heated and dehydrated in the presence or absence of a catalyst, or in the presence or absence of a solvent.
• a catalyst aromatic solvents such as benzene, toluene and medium styrene can be used.
• the catalyst include sulfuric acid, acetic acid, perat), es), acid catalysts such as boric acid, hydroxylation power) hydroxides and oxidations of alkaline earth metals such as bismuth.
• Metal oxides such as magnesium oxide, calcium oxide, etc., normal esdels such as calcium pentacarbonate, magnesium acetate, calcium acetate, etc. Catalysts can be used.
• the charging ratio of both components is not particularly limited, and is partially fumed ⁇ ⁇ ⁇ and partially methionated lon, its acid value, and the softening point of the obtained esterified product O It is usually determined in consideration of the above factors, and the strength S is usually such that the above-mentioned alcohol accounts for 10 to 15% by weight of the whole.
• the disproportionation reaction of the esdellide obtained as described above can be carried out according to various known methods. Specifically, the above esterified product may be heated to about 220 to 300 ° C. in the presence of a usual disproportionation catalyst.
• the disproportionation catalyst to be used examples include noble metals such as palladium, nickel and platinum, iodides such as iodine and iron iodide, sulfur dioxide, iron sulfide and the like. Sulfur compounds can be fisted.
• the stabilized resin used in the present invention is obtained.
• the use of the stabilized resin is an essential requirement, and the use of the stabilized resin can provide the desired effects of the present invention for the first time.
• hydrogenation may be considered in addition to the above disproportionation.
• the stabilized ⁇ -based resin used in the present invention is not limited to the above-mentioned method, and can be similarly produced, for example, by other methods described below. That is Starting from fumaric or maleated lone and disproportionating it first, followed by esterification, or disproportionation and esterification A method for simultaneously performing the steps (a) and (b) can also obtain a stabilizing resin.
• the reaction conditions and the like in each of these methods are not particularly different from known methods, and more specifically, they can conform to the methods described above.
• the stabilized lone-based resin obtained as described above usually has a softening point of 110 to 40 ° C, preferably 115 to 150 ° C.
• the softening point of the stabilized b-based resin is too low below 110 ° C or when the molecular weight is
• Heat resistance may be reduced and the cut time may be delayed. If the softening point exceeds 140 ° C and it is too high,
• the compatibility may be reduced.
• the acid value of the above resin is not particularly problematic even if it exceeds 20. However, if it is too high, the compatibility tends to slightly decrease.
• the sensitive adhesive composition of the present invention has the above-mentioned stabilized ⁇
• the resin is a tackifying resin, and is composed mainly of an ethylene copolymer and waxes. These components are mixed by heating.] .
• the ethylenic copolymer used here is a kind or two or more kinds of ethylenic acid, a vinyl ester of phenolic acid and an ester of acrylic acid. Is a copolymer with! ),
• the polar component content of the copolymer is about 10 to 60% by weight, preferably 15 to 45% by weight, and ⁇ ox (M) is 0%. 1 to 100, preferably 1 to 500.
• the latex is the number of rams that flowed out in 10 minutes at 190 ° C and a load of 216 ° C, according to -1238.
• the waxes used in the composition of the present invention include parawax and micro crystal! / Waxes Petroleum Waxes, Natural Waxes, Poly Waxes, Poly Waxes, Waxed Waxes ⁇ Pyrene waxes, etc., which can be selected as appropriate according to the intended use of the hot-melt adhesive obtained.
• the hot-melt adhesive composition of the present invention the above-mentioned ethylene copolymer, waxes and stabilized lon-based resin
• the mixing ratio of the resin is not particularly limited, and can be selected from a wide range according to the use purpose, application, and the like of the obtained hot-melt adhesive.
• the blending of the ethylene-based copolymer should be relatively low.
• Coating, layer coating, T-coating, 3 3 ⁇ 4 U coating can be used by any of various coating methods and can be used. .
• the waxes are used in an amount of 100 to 400 parts by weight based on 100 parts by weight of the ethylene-based polymer, and the stabilized resin is used in an amount of 100 to 400 parts by weight.
• the amount of the stabilizing resin is 100 to 200 parts by weight, preferably 100 to 100 parts by weight of the ethylene-based copolymer. ⁇ ! The amount is preferably in the range of 30 parts by weight and waxes in the range of 10 to 100 parts by weight, preferably 20 to 50 parts by weight.
• a four-neck flask equipped with a stirrer, a cooling pipe, a water separator, and a nitrogen inlet pipe was charged with 100 parts by weight of gamuro ⁇ and heated to 160 ° C under a nitrogen stream. It was stirred and melted.
• Reference Examples 2 to 7 Type of raw material, type of dibasic acid (fumaric acid or maleic anhydride) or its use amount, type of polyhydric alcohol or its use Various types of stabilized resin were obtained in the same manner as in Reference Example 1 except that at least one of the amounts was changed as shown in Table 1.
• composition of the present invention (Copper ') was prepared with the following composition using the stabilized resin of mouth 5 obtained in Reference Example 1, and the following compound was used to prepare the composition. Prepared test specimens
• composition of the present invention was sufficiently mixed with a peaker at 180 ° C. to obtain a composition of the present invention.
• the above composition was applied to an aluminum foil so as to have a thickness of 30 / "by using a par coater.”
• Test pieces were prepared for evaluation.
• Comparative Example 1 a comparative powder was prepared in the same manner as in Example 1, except that the following various tackifier resins were used in place of the stabilized resin obtained in Reference Example 1. Test pieces were prepared in the same manner.
• test piece width 1 inch was subjected to a peeling method.
• the load was measured at a temperature of 200 ° C. at a temperature rising rate of 5 ° C./min.
• test piece was subjected to a temperature of 180 ° C at 180 ° C for 1 kg / dsec on the base materials of wood, wood and corrugated poles for 1 to 1 hour.
• OMPI 2 ⁇ This can be peeled off by hand over time and then peeled off.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1983
  • 1983-07-27 JP JP58138526A patent/JPS6028476A/ja active Granted
• 1984
  • 1984-07-09 EP EP84902730A patent/EP0149679B1/en not_active Expired
  • 1984-07-09 US US06/717,175 patent/US4618640A/en not_active Expired - Lifetime
  • 1984-07-09 WO PCT/JP1984/000351 patent/WO1985000615A1/ja not_active Ceased
  • 1984-07-09 DE DE8484902730T patent/DE3468119D1/de not_active Expired

Patent Citations (1)

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