KR20070062299A - Hydrophilic coating solution composition for strengthening corrugating medium - Google Patents
Hydrophilic coating solution composition for strengthening corrugating medium Download PDFInfo
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- KR20070062299A KR20070062299A KR1020050122110A KR20050122110A KR20070062299A KR 20070062299 A KR20070062299 A KR 20070062299A KR 1020050122110 A KR1020050122110 A KR 1020050122110A KR 20050122110 A KR20050122110 A KR 20050122110A KR 20070062299 A KR20070062299 A KR 20070062299A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/18—Homopolymers or copolymers of nitriles
- C09D133/20—Homopolymers or copolymers of acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
Description
본 발명은 골심지 강화용 친수성 코팅액 조성물에 관한 것으로, 보다 상세하게는 아크릴아미드, 아크릴산 및 아크릴로니트릴 단량체를 라디칼 중합하여 된 하기 화학식 (1)의 랜덤(random) 삼원공중합체 또는 아크릴아미드, 아크릴산 및 양이온성 아크릴계 단량체를 라디칼 중합하여 된 하기 화학식 (2)의 구조를 갖는 랜덤(random) 삼원공중합체를 포함하는 골심지 강화용 수용성 코팅액 조성물에 관한 것이다.The present invention relates to a hydrophilic coating liquid composition for reinforcing corrugated medium, and more particularly, random terpolymer or acrylamide, acrylic acid of formula (1) obtained by radical polymerization of acrylamide, acrylic acid, and acrylonitrile monomer. The present invention relates to a water-soluble coating liquid composition for strengthening bone core, comprising a random terpolymer having a structure of the following general formula (2) obtained by radical polymerization of a cationic acrylic monomer.
화학식 (1)Formula (1)
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화학식 (2)Formula (2)
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상기 화학식 (1) 및 (2) 에서 l+ m+ n=1, R = -CH3 In formulas (1) and (2), l + m + n = 1, R = -CH 3
일반적으로 재생용지 비율이 높은 저급종이로 만들어지는 골판지는 적정한 강도와 저렴한 가격을 장점으로 각종 제품을 포장하는 포장재로 널리 사용되고 있다. 골판지를 구성하는 것은 표면과 이면에 있는 원지를 뜻하는 라이너와 상기 라이너 사이에 골을 형성하고 있는 골심지로 이루어지며, 이를 골판지 원단이라고 한다. 골판지의 제조는 전분 등을 사용하여 라이너와 골심지, 그리고 다른 라이너와의 접합을 통해 이루어지는데, 골심지는 골판지의 수직 및 수평 압축강도를 지탱하는 축으로 골판지 원단 및 상자의 강도를 가늠하는 척도가 된다. 따라서 이 골심지의 강도를 높이고 또한 강도를 유지하게 하는 것이 중요하다. 그런데, 재질의 특성상 골심지를 포함한 골판지는 다습한 조건에 약하고 원지의 함수율의 변화에 따라 강도가 급격히 저하되는 특성을 가지고 있다. In general, corrugated paper made of low-grade paper having a high ratio of recycled paper is widely used as a packaging material for packing various products with advantages of appropriate strength and low price. What constitutes corrugated cardboard consists of a liner representing the base paper on the surface and the back and a corrugated core forming a valley between the liners, which is called corrugated fabric. Corrugated cardboard is manufactured through the joining of liners, corrugated cores, and other liners using starch, etc. Corrugated cores support the vertical and horizontal compressive strength of corrugated cardboard. . Therefore, it is important to increase the strength and maintain the strength of the core wick. By the way, the corrugated paper including the corrugated core is weak in high humidity conditions and the strength of the paper decreases rapidly with the change of the moisture content of the paper.
따라서, 과실이나 야채 등 수분함량이 높은 제품이나 고온다습한 환경조건 하에서 값비싼 외국의 골판지 원지나 고지를 수입, 가공하여 적용하거나 골판지 원지의 평량(단위면적당 중량)을 높이는 방법을 사용하여 왔으나 원가상승의 부담이 크다. 상기 약점을 보강하기 위한 방법으로 합성수지 오버코팅에 의한 외부 코팅이나 라미네이션, 함침 등이 연구된 바 있다. 대한민국 특허공개공보 제2000-0050802호에는 이동하는 골판지 제조용 지지재상에 혼합고분자 수지를 스프레이 방식으로 분무ㅇ건조한 지지재를 이용하여 강도가 증진된 골판지를 제조함에 있어서, 상기 혼합고분자 수지는 요소-포름알데히드수지와 CMC인 것을 특징으로 하고, 이들의 혼입비율은 중량비로 요소-포름아데히드수지: CMC가 1:3인 것을 특징으로 하는 혼합고분자수지 처리에 의한 골판지의 강도증가 처리방법이 개시되어 있다. 또한, 대한민국 특허공개공보 제2004-0070428호에는 상단 및 하단의 파형 골 롤 표면에 홈과 골이 구성되는데 이들 표면이 보다 강한 내마모성, 내식성 그리고 내구성을 가질 수 있도록 중량%로 CR 40.0~50.0%, B 2.5~6.5%, SI 0.5~5.0%로 구성되고, C 0.0-0.5% 와 Cu, Mn, Ni, Mo, Ti, V, Zr, Hf, W의 조성물을 0.0-5.0%로 단독 또 나머지는 Fe와 필연적으로 함유되는 불순물로 구성되는 조성물질로 코팅하여 비정질 상을 갖는 골판지 제조용 파형 골 롤이 개시되어 있다.Therefore, it has been used to import and process expensive corrugated paper or paper from foreign countries which have high water content such as fruits and vegetables or high temperature and high humidity conditions, or to increase the basis weight (weight per unit area) of corrugated paper. The burden of rising is great. As a method for reinforcing the weakness, external coating, lamination, impregnation, etc. by synthetic resin overcoating have been studied. Korean Patent Laid-Open Publication No. 2000-0050802 discloses that a mixed polymer resin is prepared by using a spray-dried support material sprayed with a mixed polymer resin on a support material for manufacturing a moving cardboard, wherein the mixed polymer resin is urea-form. Disclosed is a method of increasing the strength of corrugated cardboard by a mixed polymer resin, characterized in that the aldehyde resin and the CMC, and the mixing ratio thereof is urea-formaldehyde resin: CMC 1: 3 by weight ratio. . In addition, the Republic of Korea Patent Publication No. 2004-0070428 grooves and valleys are formed on the top and bottom of the corrugated bone roll surface, CR 40.0 ~ 50.0% by weight, so that these surfaces have a stronger wear resistance, corrosion resistance and durability, B 2.5-6.5%, SI 0.5-5.0%, C 0.0-0.5% and the composition of Cu, Mn, Ni, Mo, Ti, V, Zr, Hf, W as 0.0-5.0% alone and the rest A corrugated bone roll for corrugated cardboard production having an amorphous phase by coating with a composition consisting of Fe and inevitably contained impurities is disclosed.
그러나, 상기 문헌에 개시된 방법은 상자의 용도폐기 이후 재활용이 어렵거나 불가능하게 되어 환경적으로 문제가 되어 왔다. However, the method disclosed in this document has been an environmental problem since it becomes difficult or impossible to recycle after the disposal of the box.
따라서, 본 발명이 이루고자 하는 기술적 과제는, 경제적인 방법으로 골판지의 내수성 및 지질을 향상시키고, 일정 수분의 습기에도 강도저하가 낮아 상자의 압축강도가 온습도의 영향없이 일정해지며 제품 중량을 지탱하는 자립도가 높은 강도를 제공할 수 있으면서도 친환경적인 골심지 강화용 수용성 코팅액 조성물을 제공하는 것이다.Therefore, the technical problem to be achieved by the present invention is to improve the water resistance and lipids of the corrugated cardboard in an economical way, and the strength decreases even in the moisture of a certain moisture, so that the compressive strength of the box becomes constant without the influence of temperature and humidity and to support the product weight. It is to provide a water-soluble coating liquid composition for reinforcing corrugated core while being able to provide high strength of independence.
상기 기술적 과제를 달성하기 위하여 본 발명은, 아크릴아미드, 아크릴산 및 아크릴로니트릴 단량체를 라디칼 중합한 하기 화학식 (1)의 랜덤(random) 삼원공중합체 또는 아크릴아미드, 아크릴산 및 양이온성 아크릴계 단량체를 라디칼 중합한 하기 화학식 (2)의 구조를 갖는 랜덤(random) 삼원공중합체를 포함하는 골심지 강화용 수용성 코팅액 조성물을 제공한다.In order to achieve the above technical problem, the present invention, the radical terpolymer of the following formula (1) radically polymerized acrylamide, acrylic acid and acrylonitrile monomers or radical polymerization of acrylamide, acrylic acid and cationic acrylic monomers Provided is a water-soluble coating liquid composition for reinforcing corrugation comprising a random terpolymer having a structure of Formula (2).
화학식 (1)Formula (1)
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화학식 (2)Formula (2)
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상기 화학식 (1) 및 (2) 에서 l+ m+ n=1, R = -CH3 In formulas (1) and (2), l + m + n = 1, R = -CH 3
또한, 본 발명은 상기 화학식 (1)의 랜덤(random) 삼원공중합체 중 아크릴아미드, 아크릴산 및 아크릴로니트릴 단량체의 몰비는 8.5: 1: 0.5의 조성비로 구성됨을 특징으로 하는 골심지 강화용 수용성 코팅액 조성물을 제공한다.In addition, the present invention, the molar ratio of acrylamide, acrylic acid and acrylonitrile monomer in the random terpolymer of Formula (1) is composed of a composition ratio of 8.5: 1: 0.5 water-soluble coating liquid composition for strengthening the core To provide.
또한, 본 발명은 상기 화학식 (2)의 랜덤(random) 삼원공중합체 중 아크릴아미드, 아크릴산 및 양이온성 아크릴계 단량체의 몰비는 8: 0.5: 1의 조성비로 구성됨을 특징으로 하는 골심지 강화용 수용성 코팅액 조성물을 제공한다.In addition, the present invention, the molar ratio of acrylamide, acrylic acid and cationic acrylic monomer in the random terpolymer of formula (2) is 8: 0.5: 1 water-soluble coating liquid composition for reinforcing corrugation, characterized in that the composition ratio To provide.
이하에서 본 발명에 대해 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 골심지 강화용 친수성 코팅액 조성물은 아크릴아미드, 아크릴산 및 아크릴로니트릴 단량체를 라디칼 중합하여 된 화학식 (1)의 랜덤(random) 삼원공중합체 또는 아크릴아미드, 아크릴산 및 양이온성 아크릴계 단량체를 라디칼 중합하여 된 화학식 (2)의 구조를 갖는 랜덤(random) 삼원공중합체를 포함한다. 상기 화학식 (1)의 랜덤(random) 삼원공중합체(Polyacryamide terpolymer)는 분자구조내에 아크릴아미드(acrylamide), 아크릴산(acrylic acid) 및 아크릴로니트릴(acrylonitryl)의 단위를 포함하고 있으며, 상기 단량체는 각각의 분자구조내에 -CONH2(아미드기), -COOH(카르복실기) 및 -CN(니트릴기)의 극성 작용기를 가지고 있기 때문에 친수성이며 또한 카르복실기의 이온화에 따른 음이성 특성을 가지고 있다. 화학식 (1)의 구조를 갖는 랜덤 삼원공중합체를 포함하는 본 발명의 골심지 강화용 친수성 코팅액 조성물은 상기 분자구조로 인해 산화전분과의 상용성이 우수하여 사이즈 프레스에서의 코팅이 용이하고, 골심지 섬유 조직과의 자체 수소결합에 의해 표면강도 및 종이의 강도(Stiffness)를 증가시킨다. 상기 화학식 (1)의 랜덤(random) 삼원공중합체 중 아크릴아미드, 아크릴산 및 아크릴로니트릴 단량체의 몰비는 8.5: 1: 0.5가 이상적이며, 그 허용범위는 7~8.5 : 0.5~2 : 0~0.5 의 조성비로 구성될 수 있다. 아크릴산의 경우, 적정 몰비를 벗어날 경우 이온 반발에 의한 강도 저하를 나타내고, 아크릴로 니트릴의 경우, 적정 몰비(0.5) 이상에서는 중합체의 진한색상(Yellow)으로 코팅액의 외관상 품질변화 및 강도저하를 나타낸다. The hydrophilic coating liquid composition for reinforcing corrugated medium of the present invention may be prepared by radical polymerization of a random terpolymer of formula (1) or radical polymerization of acrylamide, acrylic acid, and cationic acrylic monomers by radical polymerization of acrylamide, acrylic acid and acrylonitrile monomer Random terpolymers having the structure of formula (2). The random terpolymer (Polycryamide terpolymer) of Formula (1) includes units of acrylamide, acrylic acid and acrylonitrile in the molecular structure, each of which is a monomer It is hydrophilic because it has polar functional groups of -CONH2 (amide group), -COOH (carboxyl group) and -CN (nitrile group) in its molecular structure, and has negative properties due to ionization of the carboxyl group. Corrugated reinforcement hydrophilic coating liquid composition of the present invention comprising a random terpolymer having the structure of formula (1) is excellent in compatibility with the starch oxide due to the molecular structure is easy to coat in size press, corrugated fiber Self-hydrogen bonding with tissue increases surface strength and paper stiffness. The molar ratio of acrylamide, acrylic acid and acrylonitrile monomer in the random terpolymer of formula (1) is ideally 8.5: 1: 0.5, the acceptable range is 7-8.5: 0.5-2: 0-0.5 It may be composed of a composition ratio of. In the case of acrylic acid, the strength decreases due to ion repulsion when it is out of the appropriate molar ratio, and in the case of acrylonitrile, the apparent quality of the coating liquid and the decrease in strength are exhibited by the dark color of the polymer at a suitable molar ratio (0.5) or more.
한편, 상기 화학식 (2)의 랜덤(random) 삼원공중합체(Polyacryamide terpolymer)는 아크릴아미드(Acrylamide), 아크릴산(acrylic acid) 및 양이온성 아크릴계 단량체(cationic acrlylic monomer)를 라디칼 중합에 의해 구조적으로 random한 삼중합체로 된 고분자 화합물로 아크릴아미드의 -CONH2(아미드기), 아크릴산의 -COOH(카르복실기) 및 4급 아민계 단량체의 극성 작용기를 가지고 있어 친수성이며 또한 카르복실기의 이온화에 따른 음이성 특성과 양이온성 반복단위에 따른 양이온성을 동시에 가지고 있는 양쪽성 특성을 가지고 있다. 따라서, 화학식 (2)의 구조를 갖는 랜덤 삼원공중합체를 포함하는 본 발명의 골심지 강화용 친수성 코팅액 조성물은 상기 분자구조로 인해 산화전분과의 상용성이 우수하여 사이즈 프레스에서의 코팅이 용이하고, 골심지 섬유 조직과의 자체 수소결합에 의해 표면강도 및 종이의 강도(Stiffness)를 증가시킨다. 상기 화학식 (2)의 랜덤(random) 삼원공중합체 중 아크릴아미드, 아크릴산 및 양이온성 아크릴계 단량체의 몰비는 7~8.5 : 0.5~1 : 0.5~2의 조성비로 구성될 수 있다. 상기 조성비를 벗어나게 되면 수 이온성의 반발로 인한 강도저하 및 양이온성의 증가로 산화전분 및 내수성을 위 한 표면 사이즈제와의 상용성이 저하되어 코팅이 어렵다.Meanwhile, the random terpolymer of Formula (2) is structurally randomized by radical polymerization of acrylamide, acrylic acid, and cationic acrylic monomer. It is a high molecular compound composed of tripolymer. It has polar functional groups of acrylamide -CONH2 (amide group), acrylic acid -COOH (carboxyl group) and quaternary amine monomers. It has amphoteric properties that have cationicity in accordance with repeating units. Therefore, the hydrophilic coating liquid composition for bone core reinforcement of the present invention comprising a random terpolymer having the structure of Formula (2) is excellent in compatibility with the starch oxide due to the molecular structure, and is easy to coat in a size press. Self-hydrogen bonding with the corrugated fiber tissue increases surface strength and paper stiffness. The molar ratio of acrylamide, acrylic acid and cationic acrylic monomer in the random terpolymer of Formula (2) may be composed of a composition ratio of 7 to 8.5: 0.5 to 1: 0.5 to 2. When it is out of the composition ratio, the compatibility with the surface sizing agent for the oxidation starch and water resistance is lowered due to the decrease in strength and increase in the cationicity due to the ionic repulsion, making coating difficult.
이때, 호화농도 10%의 산화전분, 물, 아크릴 수지, 표면사이즈제, 상기 제1항 내지 제3항 중 어느 한 항에 기재된 조성물의 중량비가 각각 1:1:1:1:0.3으로 함이 가장 바람직 하다. At this time, the weight ratio of the starch oxide of 10% gelatinization concentration, water, acrylic resin, surface sizing agent, the composition according to any one of claims 1 to 3 are each 1: 1: 1: 1: 0.3 Most preferred.
본 발명의 골심지 강화용 친수성 코팅액 조성물은 골판지의 제조공정 전에 조성물 그대로 또는 사용에 적당한 형태로 스프레이나 롤러 등을 이용하여 골심지에 도포될 수 있다. The hydrophilic coating liquid composition for reinforcing corrugated medium of the present invention may be applied to the corrugated core using a spray or a roller or the like as the composition or a form suitable for use before the corrugated cardboard manufacturing process.
이하에서는 본 발명의 바람직한 태양인 실시예를 참조하여 본 발명에 대해 보다 자세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples, which are preferred embodiments of the present invention.
실시예 1(음이온성 아크릴아미드계 랜덤 삼원공중합체의 합성)Example 1 Synthesis of Anionic Acrylamide Random Terpolymer
온도계 및 냉각장치가 부착된 사구 플라스크에 일정량의 증류수를 넣고 질소가스를 주입하면서 단량체인 아크릴아미드, 아크릴산 및 아크릴로니트릴의 몰수를 8.5 : 1 : 0.5로 투입하여 완전 용해시킨 후, sodiubisulfite를 투입한 후 60℃ 로 승온시킨다. 60℃ 승온 후 Ammonium persulfate를 투입하여 80℃가 넘지 않도록 냉각하면서 발열을 제어한다. 더 이상의 발열이 없는 시전에서 약 80℃에서 2시간 반응을 지속하고 실온으로 냉각하여 pHfmf 6~7 로 보정한다. 이렇게 얻어진 음이온성 아크릴아미드계 랜덤 삼원공중합체는 고형분이 15%, pH 6~7, 점도(25℃) 4000~7000cps 이다. A certain amount of distilled water was added to a four-necked flask equipped with a thermometer and a cooling device, and nitrogen gas was injected. After that, the temperature was raised to 60 ° C. After raising the temperature to 60 ℃ Ammonium persulfate is added to control the heat generation while cooling not to exceed 80 ℃. The reaction is continued at about 80 ° C. for 2 hours in the absence of any exotherm, cooled to room temperature and calibrated to pHfmf 6-7. Thus obtained anionic acrylamide random terpolymer has a solid content of 15%, pH 6-7, and viscosity (25 degreeC) 4000-7000 cps.
실시예 2(양쪽성 아크릴 아미드계 랜덤 삼원공중합체의 합성)Example 2 (Synthesis of Amphibian Acrylamide Random Terpolymer)
실시예 1과 동일한 장치에서 아크릴아미드, 아크릴산 및 양이온성 아크릴계 단량체의 몰비를 8.5 : 0.5 : 1로 조성하여 일괄 투입한 후 동일한 개시제를 선택하여 같은 방법으로 합성한다. 이렇게 얻어진 양쪽성 아크릴아미드계 랜덤 삼원공중합체는 고형분 15%, pH 4~5, 점도(25℃) 3000~5000cps 이다.In the same apparatus as in Example 1, the molar ratio of acrylamide, acrylic acid, and cationic acrylic monomer is 8.5: 0.5: 1 and collectively added, and then the same initiator is selected and synthesized in the same manner. The amphoteric acrylamide random terpolymer obtained as described above has a solid content of 15%, a pH of 4 to 5, and a viscosity of 25 to 3000 cps.
이상에서 살펴본 바와 같이, 본 발명의 골심지 강화용 친수성 코팅액 조성물을 이용하여 코팅을 한 골심지는 내수성 및 지질이 향상되고, 재생공정시 해리가 용이하여 친환경적이다. 또한, 본 발명의 골심지 강화용 친수성 코팅액 조성물을 이용하여 코팅을 한 골심지는 일정 정도 이상의 과다수분에 노출되지 않는 한 강도저하가 낮아 상자의 압축강도가 온습도의 영향없이 일정해지며 제품 중량을 지탱하는 자립도가 높다.As described above, the core core coated with the hydrophilic coating liquid composition for strengthening the core core of the present invention is improved in water resistance and lipids, and is easy to dissociate during the regeneration process and is environmentally friendly. In addition, the core core coated with the hydrophilic coating liquid composition for strengthening the core core of the present invention has a low strength decrease unless exposed to excessive moisture to a certain degree, so that the compressive strength of the box is constant without the influence of temperature and humidity, and supports the product weight. Independence degree is high.
앞에서 설명되고, 도면에 도시된 본 발명의 일실시예는 본 발명의 기술적 사상을 한정하는 것으로 해석되어서는 안 된다. 본 발명의 보호범위는 청구범위에 기재된 사항에 의하여만 제한되고, 본 발명의 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상을 다양한 형태로 개량 변경하는 것이 가능하다. 따라서 이러한 개량 및 변경은 통상의 지식을 가진 자에게 자명한 것인 한 본 발명의 보호범위에 속하게 될 것이다.An embodiment of the present invention described above and illustrated in the drawings should not be construed as limiting the technical spirit of the present invention. The protection scope of the present invention is limited only by the matters described in the claims, and those skilled in the art can change and change the technical idea of the present invention in various forms. Therefore, such improvements and modifications will fall within the protection scope of the present invention, as will be apparent to those skilled in the art.
Claims (4)
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR850001344A (en) * | 1983-07-16 | 1985-03-18 | 최식림 | Method of manufacturing reinforced corrugated core |
| KR900002929A (en) * | 1988-08-31 | 1990-03-23 | 박병웅 | Corrugated cardboard |
| JPH05163697A (en) * | 1991-12-19 | 1993-06-29 | Mitsui Toatsu Chem Inc | Agent for improving surface strength of paper |
| JPH10202772A (en) * | 1997-01-27 | 1998-08-04 | Oji Paper Co Ltd | Moisture-proof corrugated carton and manufacture thereof |
| KR19990044129A (en) * | 1995-08-25 | 1999-06-25 | 마이클 제이. 켈리 | Paper printability and strength improvement method and improving agent |
| KR20000060064A (en) * | 1999-03-11 | 2000-10-16 | 윤병옥 | Strength reinforcing agent of corrugated medium paper for corrugated fiberboard and corrugated fiberboard manufacturing process using the same |
-
2005
- 2005-12-12 KR KR1020050122110A patent/KR20070062299A/en not_active Application Discontinuation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR850001344A (en) * | 1983-07-16 | 1985-03-18 | 최식림 | Method of manufacturing reinforced corrugated core |
| KR900002929A (en) * | 1988-08-31 | 1990-03-23 | 박병웅 | Corrugated cardboard |
| JPH05163697A (en) * | 1991-12-19 | 1993-06-29 | Mitsui Toatsu Chem Inc | Agent for improving surface strength of paper |
| KR19990044129A (en) * | 1995-08-25 | 1999-06-25 | 마이클 제이. 켈리 | Paper printability and strength improvement method and improving agent |
| JPH10202772A (en) * | 1997-01-27 | 1998-08-04 | Oji Paper Co Ltd | Moisture-proof corrugated carton and manufacture thereof |
| KR20000060064A (en) * | 1999-03-11 | 2000-10-16 | 윤병옥 | Strength reinforcing agent of corrugated medium paper for corrugated fiberboard and corrugated fiberboard manufacturing process using the same |
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