Articles coated with polyisobutylene-polyolefin films

Abstract

To provide an article in which waterproof steam characteristics and recycling suitability are imparted to paper or paperboard.SOLUTION: An article comprising a film applied to a paper or paperboard substrate, wherein the film comprises polyisobutylene and polyolefin, and wherein the film has a thickness in the range of about 3 μm to 20 μm. The article is useful for providing desirable moisture barrier and adhesion properties.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a paper coated with a combination of polyisobutylene and polyolefin. or paperboard. The coating provides vapor barrier properties to these substrates. [Background technology]

[0002] Moisture-proof properties are traditionally achieved by applying a coating, usually molten polyethylene, onto a paper substrate, It is then cooled and calendered to apply to the paper or paperboard. Ethylene is heat sealable, flexible, and omniphobic. Nevertheless, as is standard in the industry, polyethylene Coated paper and paperboard have several drawbacks. First, they lack the desired moisture barrier properties. to achieve adhesion to the substrate and avoid film defects such as pinhole leaks A thick coating, typically about 1 mil (25 microns), must be applied to the substrate. Alternatives to polyethylene, such as acrylic, do not provide acceptable moisture barrier properties. Acrylic, unlike polyethylene, is not easily heat-sealable. Polyvinylidene chloride (PVDC) is another alternative, which has low It provides excellent moisture resistance at low weight, but decomposes at low temperatures, causing contamination of recycled materials and This can cause corrosion and damage to material recycling equipment.

[0003] Therefore, in the field of paper and paperboard coating, it is necessary to save on raw material costs. In addition, the coatings required today to make the coated products suitable for recycling It would be advantageous to achieve acceptable moisture barrier properties at a fraction of the standard film thickness used. Furthermore, even a weight loss of only 2% by weight of the final product (e.g., paper cup) would be , which has a significant impact on transportation costs. Summary of the Invention

[0004] In one aspect, the present invention provides an article comprising a film attached to a paper or paperboard substrate. , the film is 20 to 80 weight percent polyisobutylene and 20 to 80 weight percent and a polyolefin, wherein the film has a thickness in the range of about 3 μm to 20 μm. This invention addresses a need in the art by providing an article that

[0005] In a second aspect, the present invention provides a composition comprising: a) polyisobutylene particles; and b) polyisobutylene particles. The polyolefin particles may be ethylene particles or polypropylene particles, and the polyolefin particles may be an aqueous dispersion of the polyolefin particles. The weight-to-weight ratio of isobutylene particles to polyolefin particles is 20:80-80 20% by weight of the composition, and the composition contains 20 to 60% by weight of polyisobutylene particles and polyisobutylene particles. and a solids content resulting from polyolefin particles, The fine particles are in the range of 0.1μm to 12μm. 90 The composition has a particle size. DETAILED DESCRIPTION OF THE INVENTION

[0006] In a first aspect, the present invention is an article comprising a film attached to a paper or paperboard substrate. The film is made of 20 to 80 weight percent polyisobutylene and 20 to 80 weight percent and a polyolefin, and the film has a thickness in the range of about 3 μm to 20 μm. It is an item that has something.

[0007] The article of the present invention comprises a paper or paperboard substrate comprising polyisobutylene and polyolefin polymer particles. coating the substrate with an aqueous dispersion of the compound, followed by removal of the water as described herein. The polyisobutylene and polyolefin polymer particles can be prepared by the method of The aqueous dispersion is advantageously a mixture of an aqueous dispersion of polyisobutylene polymer particles and a polyolefin polymer. It is prepared by blending an aqueous dispersion of polyisobutylene polymer particles with an aqueous dispersion of polyisobutylene polymer particles. Aqueous dispersions of polymer particles can be transformed into resinous flows under high shear conditions in the presence of suitable surfactants. The polymer may be prepared by dispersing the polymerizable polyisobutylene in water. When used, "polyisobutylene" refers to isobutylene homopolymer as well as isobutylene copolymer. The copolymer contains repeating units of butylene and comonomers, with the majority of repeating units being isobutylene. It refers to a copolymer that forms a polymer. An example of a copolymer is poly(isobutylene-isopropyl) Examples of suitable polyisobutylene include poly(isobutylene-succinic anhydride), commercially available polyisobutylene ( Examples of homopolymers and copolymers (also called polyisobutene) include Oppano l B10, Oppanol B12, Oppanol B15, Oppanol B1 00, and Oppanol B200 polyisobutylene, Glissopal V190 , Glissopal V500, Glissopal V640, and Glissop al V1500 Polyisobutene, Vistanex LM-MH, Vistanex LM-MS, LM-H Polyisobutene, Laxess X Butyl RB 100, Laxe ss X Butyl RB 101-3, and Laxess X Butyl RB 402 Isobutyl ethylene-isoprene copolymer, as well as HRD-350, HRD-400, HRD-450, HRD-500, HRD-600, HRD-650, and HRD 950 Polyisobutylene Examples include:

[0008] Examples of suitable surfactants include alkali metal C8-C 20 -Alkylbenzene sulfonate Anionic surfactants such as esters and sulfates, and secondary alcohol ethoxylates C8~C 20 - Nonionic surfactants such as alkyl glucosides. Specific examples of suitable anionic surfactants include sodium dodecylbenzenesulfonate. and sodium dodecylbenzene sulfate. Secondary alcohol ethoxylates include: The following formula [ka] where x is 8 to 50 and O(CH2CH2O) x H group is C 10~15 H 22~32 It is preferably bonded to a CH group on the chain. Coal ethoxylate has the following formula: [ka] In the formula, x is preferably 10 to 50, preferably 10 to 40. A commercially available example of a suitable surfactant is TERGITOL™ 15-S -40, TERGITOL 15-S-20, and TERGITOL TMN-10 Grade II Alcohol ethoxylate surfactants (The Dow Chemical Company) ny or its affiliates). Suitable alkyl glucosides include decyl Examples of suitable glycerols include glycerol glucoside, dodecyl glucoside, and lauryl glucoside.

[0009] D of dispersed polyisobutylene polymer particles 90 Particle size was measured using a dynamic light scattering particle size analyzer (e.g., Beckman LS230 Particle Size Analyzer When determined by the above method, it is from 0.1 μm, preferably from 0.2 μm, more preferably from 0. From 5 μm to 12 μm, preferably to 8 μm, more preferably to 4 μm, most preferably Preferably, it is in the range of up to 2 μm.

[0010] Aqueous dispersions of polyolefin particles are disclosed in U.S. Pat. No. 8,318,257 and U.S. Pat. No. 7,888,258. prepared by a continuous twin-screw extrusion process such as that described in US Pat. No. 03865. Dispersions of polyolefin polymer particles may be prepared, for example, by methods disclosed in U.S. Pat. As described in No. 3, the polymer is mixed in the presence of a dispersant, a neutralizing agent, and a coupling agent. The dispersant may be prepared by dispersing particles. The dispersant preferably has an ethylene structure. Copolymers containing structural units of ethylene-carboxylic acid monomers and structural units of carboxylic acid monomers (i.e., ethylene-carboxylic acid copolymers). The copolymer has a melting point of 50g / 10min to 2000g / 10min. and a structure of carboxylic acid monomers of ethylene structural units. The weight-to-weight ratio for the units ranges from 95:5 to 70:30. The test range is 190°C and 2.16 kg load, according to ASTM 1238. The range is determined by the

[0011] As used herein, suitable polyolefin particles have a wide molecular weight range. but does not include polyolefin wax, which has the following formula: [ka] wherein R is H or CH3 and x is a number between 72 and 360. It's in range.

[0012] The neutralizing agent may be an inorganic base or an organic base. Examples of suitable inorganic bases include ammonium hydroxide, ammonium nitrate ... Suitable hydroxides include ammonium hydroxide, potassium hydroxide, sodium hydroxide, and calcium hydroxide. Examples of organic bases include N,N-dimethylethanolamine, diethylamine, and mol The concentration of the neutralizing agent is preferably such that at least 10% of the carboxylic acid groups in the dispersant are For example, if the dispersant contains 0.05 moles of carboxylic acid groups, the In this case, at least 0.025 moles of a neutralizing agent such as N,N-dimethylethanolamine is required. Therefore, the basic functional group in the neutralizing agent, preferably an amine group or an amine group, may be required. The ratio of amine to carboxylic acid groups in the dispersant is preferably at least 0.5:1. The composition prepared using the dispersant and the neutralizing agent may contain the neutralizing agent, or a salt thereof, or Includes a combination of:

[0013] A coupling agent is included to improve compatibility between the dispersant and the polyolefin. An example of a suitable coupling agent is ethylene-co-maleic anhydride. If used, the weight of the polyolefin, dispersant, and coupling agent is As a result, it is 5 to 20 weight percent, more preferably 10 weight percent or less. It is present in concentrations ranging from .

[0014] Dispersed polyolefin particles D 90 Particle size was also determined using a dynamic light scattering particle size analyzer. If so, it is from 0.1 μm, preferably from 0.2 μm, more preferably from 0.5 μm , up to 12 μm, preferably up to 8 μm, more preferably up to 4 μm, most preferably up to 2 μm The range is up to μm.

[0015] The polyolefin dispersion is a polypropylene dispersion or a polyethylene dispersion. When used in the specification, "polyethylene" refers to linear low-density polyethylene, low-density polyethylene, polyethylene, high density polyethylene, ethylene-co-octene copolymer, ethylene-co-hexene ethylene-alkene copolymers, such as ethylene-propylene copolymers, -, ethylene-methyl acrylate copolymer, or ethylene-ethyl acrylate copolymer ethylene-carboxylic acid ester copolymers such as ethylene-methacrylic acid; It refers to ethylene-carboxylic acid copolymers, as well as combinations thereof. If the carboxylic acid copolymer has an acid number of less than 90 mg KOH / g, it is considered to be polyethylene. is considered to be.)

[0016] A commercially available example of an aqueous polyethylene dispersion is CANVERA™ 1110 Polyolefin. FINN dispersion, HYPOD™ 2000 polyolefin dispersion, and RHOBARR (TM) 320 Polyolefin Elastomer Dispersion (CANVERA, HYPOD, and RHOBARR is a registered trademark of The Dow Chemical Company or its affiliates. are trademarks of the company.

[0017] As used herein, polypropylene includes polypropylene homopolymer, as well as It contains repeating units of polypropylene and comonomer, and the polypropylene repeating units are comonomers. Refers to a copolymer that forms the majority of the polymer.

[0018] of polyisobutylene polymer particles, polyolefin polymer particles, preferably polyethylene The weight to weight ratio of the polyethylene polymer particles is preferably 25:75 to 70:30, more preferably Preferably in the range of up to 65:35.

[0019] After the dispersions are combined, the composition is applied to the paper or paperboard using a wire-wound drawdown bar. Advantageously, the wet film can be applied at a temperature of preferably from 50°C, more preferably from or a temperature ranging from 70°C, preferably up to 150°C, more preferably up to 120°C. to remove water and form a dry coating, from 8 μm, more preferably from 20 μm, preferably from 16 μm, more preferably This provides a final dry film having a thickness ranging from 10 to 12 μm.

[0020] In another aspect, the present invention is an article comprising a film attached to a paper or paperboard substrate. The film comprises 20 to 80 weight percent polyisobutylene polymer and 20 to 80 and a polyolefin which is polyethylene or polypropylene in weight percent, The film has a thickness in the range of about 4 μm to 20 μm. Polymers include polyisobutylene polymers and polyethylene as defined herein above. In the film, the polyisobutylene polymer is preferably a polyolefin polymer, preferably a polyethylene The weight to weight ratio of the polyethylene polymer is preferably 25:75 to 70:30, more preferably or in the range of 65:35.

[0021] The weight density of the paper or paperboard is 40 g / m 2 ~350g / m 2 In the case of paper, the preferred The preferred weight density is 60 g / m 2 ~100g / m 2 In the case of paperboard, the preferred range is Weight density is 200g / m 2 ~300g / m 2 The paper or paperboard is coated It may be uncoated or coated to produce a smooth surface prior to application of the coating formulation. The material may be pre-coated.

[0022] Thin coatings of polyisobutylene-polyolefin films on paper or paperboard substrates It has been found to provide desirable vapor barrier properties combined with an acceptable low level of adhesion. Coated substrates are often recycled for recycling purposes. Suitable for packaging applications requiring a relatively low fat to substrate weight ratio. do.

[0023] Example Example 1 - Polyisobutylene Resin Dispersion A (PIBD) e. Preparation of Resin Dispersion (A) HRD-400 Polyisobutylene Resin (50g, Shandong Hongrui Powered by New Material Technology Co., Inc. TERGITOL™ TMN-10 dispersion (2.8 g, 90% active ingredient) and Combine with water (2.2g) and mix in a FlackTek SpeedMixer DAC 150. 1 FV-K was used to mix at 3500 rpm for 4 minutes. Then, while stirring, of water (45 g) was slowly added to prepare a 50% solids solution with a D 90 particle size An aqueous polyisobutylene (PIB) dispersion was formed.

[0024] Example 2 - Preparation of Polyisobutylene Resin Dispersion B (PIBD-B) HRD-400 polyisobutylene resin (50g), TERGITOL™ 15-s The 2.5 g of 1000-9 dispersion and 2.5 g of water were combined and mixed in a FlackTek SpeedM Mixed using a IXER DAC 150.1 FV-K at 3500 rpm for 4 minutes. Then, additional water (45 g) was added slowly with stirring to a final concentration of 50% solids, 1.03 μL. D of m 90 An aqueous PIB dispersion having particle sizes was formed.

[0025] Example 3 - Preparation of Polyisobutylene Resin Dispersion C (PIBD-C) HRD-400 polyisobutylene resin (50g) and Plantacare 2000 Combined with UP decyl glucoside (5g, active ingredient 50%, supplied by BASF) , using FlackTek SpeedMixer DAC 150.1 FV-K The mixture was mixed at 3500 rpm for 4 minutes. Additional water (45 g) was then added slowly with stirring. In addition, 50% solids content, 1.02 μm D 90 Aqueous PIB dispersion with particle size was formed. Successful.

[0026] Example 4 - Preparation of Polyisobutylene Resin Dispersion D (PIBD-D) HRD-400 polyisobutylene resin (50g) and DS-4 dodecylbenzene sulfonate Sodium phosphate (5g, 23% active ingredient) and FlackTek SpeedMi The mixture was mixed using a Xer DAC 150.1 FV-K at 3500 rpm for 4 minutes. Additional water (45 g) was then added slowly with stirring to a final solids content of 50%, 0.8 7 μm D 90 An aqueous PIB dispersion having particle sizes was formed.

[0027] CANVERA 1110 polyolefin dispersion (CANV, 43% solids), or R HOBARR 320 polyolefin dispersion (RHOB, 43% solids) was heated at ambient temperature The IB dispersion was combined to form the composition described in Table 1. All amounts listed are based on solids content. The total dispersion is in grams unadjusted for weight. [Table 1]

[0028] The coating formulation was prepared by blending the ingredients at room temperature. The film was then applied to a paper sheet with a wire bar using a Meyer bar automatic film coating device. Coated (60g / m 2 ) The coated film was dried at 100°C for 2 minutes. The thickness of the dry film was controlled to 10±2 μm.

[0029] Table 2 shows the water vapor transmission rate (WVTR) performance at 38°C and 90% relative humidity. R is MOCON TRAN Model 3 / 33 Permeation Anal yzer at 38°C and 90% relative humidity according to ASTM D3985-02 Comparative Example 3 is a pure PIB dispersion. PT-1000 probe tack Using a tester, the film adhesion was measured at a probe speed of 0.5 cm / sec and a dwell time of 1 sec. The WVTR was evaluated in g / m 2 The WVTR reduction was measured in days. , and for coatings from the corresponding unblended PE dispersions in 4 , refers to the percent reduction in WVTR of coatings from PB / PE blends. [Table 2]

[0030] The data show that coatings formed from polyethylene dispersions alone exhibit poor WVTR (100g / m 2 In contrast, 100g / m 2 · WVTR of less than 1 day was achieved from PIB dispersion alone or from a blend of PIB and PE dispersions. However, as shown in Table 3, The proper balance between WVTR and probe adhesion is achieved by the coating formed from the blend. Probe tack is measured in grams. Low tack requires paper coating. This is necessary for feeding applications. [Table 3]

[0031] PIBD-A and CANVERA 1110 Polio, a dispersion in high-density polyethylene. Coatings resulting from blends with olefin dispersions have excellent adhesion over a wide range of In contrast, the coatings produced from PIBD-A alone exhibited poor It only gave sufficient stickiness (more than 4.5 g).

Claims

1. 1. An article comprising a film attached to a paper or paperboard substrate, said film comprising: up to 80 weight percent polyisobutylene and 20 to 80 weight percent polyolefin and wherein the film has a thickness in the range of about 3 μm to 20 μm.

2. The polyolefin is polyethylene, and the polyisobutylene is polyisobutylene. The article of claim 1 which is a homopolymer.

3. a weight to weight ratio of the polyisobutylene homopolymer to the polyethylene of 2 3. The article of claim 2, wherein the ratio is in the range of 5:75 to 70:

30.

4. a weight to weight ratio of the polyisobutylene homopolymer to the polyethylene of 2 3. The article of claim 2, wherein the ratio is in the range of 5:75 to 65:

35.

5. The polyethylene is an ethylene-co-octene copolymer or an ethylene-acrylic copolymer.

5. The method of claim 1, further comprising the step of: Goods.

6. 5. The method of claim 1, wherein the polyethylene comprises high density polyethylene. Goods.

7. The article of claim 1 further comprising a dispersant and a coupling agent.

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